WO2023020314A1 - 一种非水电解液及锂电池 - Google Patents

一种非水电解液及锂电池 Download PDF

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Publication number
WO2023020314A1
WO2023020314A1 PCT/CN2022/110794 CN2022110794W WO2023020314A1 WO 2023020314 A1 WO2023020314 A1 WO 2023020314A1 CN 2022110794 W CN2022110794 W CN 2022110794W WO 2023020314 A1 WO2023020314 A1 WO 2023020314A1
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additive
lithium
formula
electrolytic solution
carbon atoms
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English (en)
French (fr)
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陈晓琴
甘朝伦
时二波
张力
卢晓锋
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Priority to EP22857626.0A priority Critical patent/EP4391135A4/en
Priority to US18/555,825 priority patent/US20240222705A1/en
Publication of WO2023020314A1 publication Critical patent/WO2023020314A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/0568—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
    • H01M10/056—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
    • 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 a non-aqueous electrolytic solution and a lithium battery.
  • lithium-ion batteries With the emergence of emerging consumer fields such as mobile phones, tablet computers, smart wearables, and ETC, lithium-ion batteries have shown great advantages due to their high energy density and long cycle life.
  • the wide application of lithium-ion batteries requires that lithium-ion batteries can adapt to different use environments and maintain good performance in different harsh environments. Higher temperature and higher rate use range have become important issues for the development of lithium-ion batteries .
  • Electrolyte as the blood of lithium-ion batteries, has a great influence on the performance of lithium-ion batteries.
  • film-forming additives are usually added to the electrolyte, such as adding vinylene carbonate to the electrolyte, which can When the battery is formed, a better film is formed on the surface of the battery electrode to prevent the further progress of the reaction, thereby improving the cycle performance of the battery.
  • the film formed by adding vinylene carbonate is easily decomposed at high temperature, causing the battery to be damaged at high temperature. cannot function.
  • additives such as lithium bisoxalate borate will be added to the electrolyte. Lithium bisoxalate borate can form a better film at high temperature, but due to the large thickness of the film and the relatively low conductivity of the film It will cause the internal resistance of the battery to be too large, thereby affecting the battery capacity and other performances.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a non-aqueous electrolytic solution with excellent high temperature, cycle and rate performance.
  • the invention also provides a lithium battery with excellent performance in high temperature, cycle and rate.
  • the present invention provides a kind of non-aqueous electrolytic solution on the one hand, comprises lithium salt, organic solvent and additive, and described additive comprises additive A and additive B, and the chemical structural formula of described additive A is as shown in formula (1), and described formula ( 1) for Wherein, the X, the Y, and the Z are independently selected from O, S, N, P, Any one of them, said n is a positive integer, said R is selected from any one of hydrogen, halogen, alkyl, cyano, haloalkyl, haloalkoxy, and said R is selected from hydrogen, halogen , alkyl, haloalkyl, cyano, siloxane, alkoxy, and haloalkoxy, and R is selected from alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy phenylalkenyloxy, alkenylene, haloalkenylene, alkenyleneoxy, haloalkenyleneoxy, al
  • the additive B includes one or more of the first additive B, the second additive B and the third additive B,
  • the chemical structural formula of the first additive B is shown in formula (2), and the formula (2) is Wherein, said m and said p are independently selected from any of 0, 1, and 2, and said A, said B, and said D are each independently selected from among O, S, N, and P.
  • the chemical structural formula of the second additive B is shown in formula (3), and the formula (3) is Wherein, the a, the b, the c, the d, and the e are independently selected from 0, 1, and 2, and the E, the G, the L, and the J are independently One or more groups or alkyl groups selected from O, S, N, and P;
  • the chemical structural formula of the third additive B is shown in formula (4), and the formula (4) is Wherein, the R 4 and the R 5 are independently selected from any one of hydrogen, alkyl, halogen, and alkoxy, and the x is selected from any one of 0, 1, and 2.
  • the halogen used in the present invention or the halogen used for halogenation is one or more of fluorine, chlorine, bromine and iodine, preferably fluorine.
  • the X, the Y, and the Z in the formula (1) are independently selected from N or
  • the n is selected from any one of 1, 2, 3, and 4, and the R 3 is hydrogen or an alkyl group with 1 to 5 carbon atoms.
  • the X and Y in the formula (1) are The Z is selected from N or The n is selected from 1 or 2, and the R 3 is hydrogen or an alkyl group with 1 to 3 carbon atoms.
  • the R 1 in the formula (1) is hydrogen or an alkyl group with 1 to 5 carbon atoms.
  • the R 1 in the formula (1) is hydrogen or an alkyl group with 1 to 3 carbon atoms.
  • the R in the formula (1) is selected from the group consisting of alkenyleneoxy groups with 1 to 5 carbon atoms, alkenyloxy groups with 1 to 5 carbon atoms, benzene with 8 to 12 carbon atoms Any of alkenyloxy, alkynyl having 1 to 5 carbon atoms, and alkynyloxy having 1 to 5 carbon atoms.
  • the additive A includes 1H-imidazole-1-carboxylate-2-propenyl ester, 3,5-dimethylpyrazole-1-carboxylate allyl ester, 3-phenylpropyl -2-en-1-yl 1H-imidazole-1-carboxylate, allyl 2,3-dihydro-1H-pyrrole-1-carboxylate, allyl 1H-pyrrole-1-carboxylate , 2-propyn-1-yl 1H-imidazole-1-carboxylate, 1-imidazol-1-ylpentan-4-in-1-one or one or more.
  • the additive A includes 1H-imidazole-1-carboxylate-2-propenyl ester, 3,5-dimethylpyrazole-1-carboxylate allyl ester, 3-phenylpropane-2- En-1-yl 1H-imidazole-1-carboxylate, allyl 2,3-dihydro-1H-pyrrole-1-carboxylate, allyl 1H-pyrrole-1-carboxylate, 2- One or more of propyn-1-yl 1H-imidazole-1-carboxylates.
  • the additive A accounts for 0.01-2%, further 0.1-1.5%, and further 0.5-1% of the total mass of the non-aqueous electrolyte.
  • the A, the B, and the D in the formula (2) are each independently selected from O or an alkyl group with 1 to 3 carbon atoms.
  • the E, the G, the L, and the J in the formula (3) are each independently selected from O or an alkyl group with 1 to 3 carbon atoms.
  • the R 4 and the R 5 in the formula (4) are independently selected from hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • the additive B includes propylene sulfate, vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, methylene disulfonate One or more of esters, pentaerythritol sulfate.
  • the additive B includes one or more of vinyl sulfate, methylene methanedisulfonate, and pentaerythritol sulfate.
  • the additive B accounts for 0.01-5%, further 0.1-3%, further 0.5-2%, and further 1-1.5% of the total mass of the non-aqueous electrolyte.
  • the additive further includes succinonitrile and/or fluoroethylene carbonate.
  • the succinonitrile accounts for 1-3% of the total mass of the non-aqueous electrolyte solution, and further is 1.5-2.5%.
  • the fluoroethylene carbonate accounts for 3-5% of the total mass of the non-aqueous electrolytic solution, furthermore 3.5-4.5%.
  • the organic solvent is a cyclic ester and/or a chain ester
  • the cyclic ester is one or more of ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate
  • the chain ester is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, One or more of propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, ethyl fluoropropionate, and ethyl fluoroacetate.
  • the organic solvent is a mixture of cyclic esters and chain esters, wherein the volume ratio of the cyclic esters and the chain esters is 1: (1-2.5).
  • the cyclic ester and the chain ester are mixed at a volume ratio of 1:(1.5-2).
  • the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis(trifluoromethylsulfonyl)imide, lithium difluorodioxalate phosphate, One or more of lithium fluorophosphate, lithium trifluoromethanesulfonate, lithium difluorodioxalate phosphate, lithium dioxalate borate, monooxalate lithium difluoroborate, and lithium difluorosulfonyl imide.
  • the concentration of the lithium salt is 0.6-1.5 mol/L, further 0.8-1.3 mol/L, further 1-1.2 mol/L.
  • a lithium battery including a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the above-mentioned non-aqueous electrolyte.
  • the positive electrode is a lithium cobalt oxide positive electrode material.
  • the negative electrode is graphite material.
  • the lithium battery is a high-voltage lithium battery of 4.35V or above.
  • the present invention has the following advantages compared with the prior art:
  • the present invention solves the problems of easy decomposition of non-aqueous electrolytic solution at high temperature, poor high-temperature cycle performance and poor rate performance by adding additive A and additive B to the non-aqueous electrolytic solution.
  • Lithium batteries with non-aqueous electrolytes have excellent high temperature performance, cycle performance, and rate performance.
  • Lithium batteries are widely used due to their advantages of fast response, two-way regulation, high energy, long life, and flexible configuration. With the wide application, higher requirements are placed on the performance of lithium batteries. It is also required that the lithium battery can have good cycle performance and rate performance when used in a temperature range. Based on this, the inventor of this case has been able to propose the technical solution of the present invention through long-term research and extensive practice.
  • An embodiment of the present invention provides a non-aqueous electrolytic solution, including lithium salt, organic solvent and additives.
  • Described additive comprises additive A and additive B, and the chemical structural formula of described additive A is as shown in formula (1), and described formula (1) is Wherein, the X, the Y, and the Z are independently selected from O, S, N, P, Any one of them, said n is a positive integer, said R is selected from any one of hydrogen, halogen, alkyl, cyano, haloalkyl, haloalkoxy, and said R is selected from hydrogen, halogen , alkyl, haloalkyl, cyano, siloxane, alkoxy, and haloalkoxy, and R is selected from alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy phenylalkenyloxy, alkenylene, haloalkenylene, alkenyleneoxy, haloalkenyleneoxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy
  • the additive B includes one or more of the first additive B, the second additive B and the third additive B,
  • the chemical structural formula of the first additive B is shown in formula (2), and the formula (2) is Wherein, said m and said p are independently selected from any of 0, 1, and 2, and said A, said B, and said D are each independently selected from among O, S, N, and P.
  • the chemical structural formula of the second additive B is shown in formula (3), and the formula (3) is Wherein, the a, the b, the c, the d, and the e are independently selected from 0, 1, and 2, and the E, the G, the L, and the J are independently One or more groups or alkyl groups selected from O, S, N, and P;
  • the chemical structural formula of the third additive B is shown in formula (4), and the formula (4) is Wherein, the R 4 and the R 5 are independently selected from any one of hydrogen, alkyl, halogen, and alkoxy, and the x is selected from any one of 0, 1, and 2.
  • the present invention adds additive A and additive B to the non-aqueous electrolytic solution, and through the synergistic effect between additive A and additive B, the high-temperature cycle performance of the lithium battery is increased while reducing the decomposition of the non-aqueous electrolytic solution at high temperature, and the lithium The DC impedance of the battery can remain basically unchanged.
  • the X, the Y, and the Z in the formula (1) are independently selected from N or
  • the n is selected from any one of 1, 2, 3, and 4, and the R 3 is hydrogen or an alkyl group with 1 to 5 carbon atoms.
  • the X and the Y in the formula (1) are The Z is selected from N or The n is selected from 1 or 2, and the R 3 is hydrogen or an alkyl group with 1 to 3 carbon atoms.
  • R 1 in the formula (1) is hydrogen or an alkyl group with 1 to 5 carbon atoms.
  • R 1 in the formula (1) is hydrogen or an alkyl group with 1 to 3 carbon atoms.
  • R in the formula (1) is selected from the group consisting of alkenyleneoxy groups with 1 to 5 carbon atoms, alkenyloxy groups with 1 to 5 carbon atoms, benzene with 8 to 12 carbon atoms Any of alkenyloxy, alkynyl having 1 to 5 carbon atoms, and alkynyloxy having 1 to 5 carbon atoms.
  • the additive A includes 1H-imidazole-1-carboxylic acid-2-propenyl ester Allyl 3,5-Dimethylpyrazole-1-carboxylate 3-Phenylprop-2-en-1-yl 1H-imidazole-1-carboxylate Allyl 2,3-dihydro-1H-pyrrole-1-carboxylate Allyl 1H-pyrrole-1-carboxylate 2-propyn-1-yl 1H-imidazole-1-carboxylate 1-imidazol-1-ylpentan-4-in-1-one one or more of.
  • the additive A includes 1H-imidazole-1-carboxylate-2-propenyl ester, 3,5-dimethylpyrazole-1-carboxylate allyl ester, 3-phenylprop-2-ene -1-yl 1H-imidazole-1-carboxylate, allyl 2,3-dihydro-1H-pyrrole-1-carboxylate, allyl 1H-pyrrole-1-carboxylate, 2-propane One or more of alkyn-1-yl 1H-imidazole-1-carboxylates.
  • additive A accounts for 0.01-2% of the total mass of the non-aqueous electrolyte, further 0.1-1.5%, and still further 0.5-1%.
  • Additive A in the present invention has a small amount of addition and good effect.
  • the A, the B, and the D in the formula (2) are each independently selected from O or an alkyl group with 1 to 3 carbon atoms.
  • the E, the G, the L, and the J in the formula (3) are each independently selected from O or an alkyl group with 1 to 3 carbon atoms.
  • R 4 and the R 5 in the formula (4) are independently selected from hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • the additive B includes propylene sulfate, vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, methylene disulfonate, pentaerythritol sulfate one or more of esters.
  • the additive B includes one or more of vinyl sulfate, methylene methanedisulfonate, and pentaerythritol sulfate.
  • the additive B accounts for 0.01-5%, further 0.1-3%, further 0.5-2%, and further 1-1.5% of the total mass of the non-aqueous electrolyte.
  • the additives also include succinonitrile and/or fluoroethylene carbonate.
  • the succinonitrile accounts for 2% of the total mass of the non-aqueous electrolyte.
  • the fluoroethylene carbonate accounts for 4% of the total mass of the non-aqueous electrolyte.
  • the organic solvent is a cyclic ester and/or a chain ester, and the cyclic ester is one or more of ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate;
  • the Chain esters are dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate , methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, ethyl fluoropropionate, and ethyl fluoroacetate.
  • other unlisted organic solvents in the field of lithium batteries are also suitable for the electrolyte solution of the present invention.
  • the organic solvent is a mixture of cyclic esters and chain esters, wherein the volume ratio of the cyclic esters and the chain esters is 1: (1-2.5).
  • the cyclic ester and the chain ester are mixed at a volume ratio of 1: (1.5 to 1.8); when the additive does not include When using succinonitrile and/or fluoroethylene carbonate, the cyclic ester and the chain ester are mixed at a volume ratio of 1: (1.8-2.5).
  • the combination of cyclic esters and chain esters in the present invention can be arbitrarily taking more than one cyclic ester in cyclic esters and combining arbitrarily taking more than one chain esters in chain esters, for example, It can be a combination of randomly selecting two kinds of cyclic esters from the cyclic esters and randomly selecting one chain ester from the chain esters. Two kinds of chain esters are randomly selected for combination.
  • the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate anhydrous, lithium bis(trifluoromethylsulfonyl)imide, lithium difluorodioxalate phosphate, lithium difluorophosphate , Lithium trifluoromethanesulfonate, Lithium difluorodioxalate phosphate, Lithium dioxalate borate, Lithium difluoroborate monooxalate, Lithium bisfluorosulfonyl imide.
  • any lithium salt commonly used in electrolytes for lithium batteries can also be used in the present invention.
  • the lithium salt is lithium hexafluorophosphate.
  • the concentration of the lithium salt is 0.6-1.5 mol/L.
  • the concentration of the lithium salt is 1 mol/L.
  • An embodiment of the present invention also provides a lithium battery, including a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte is the above-mentioned non-aqueous electrolyte.
  • the positive electrode is lithium cobalt oxide positive electrode material.
  • the negative electrode is made of graphite material.
  • the lithium battery is a high-voltage lithium battery of 4.35V or above.
  • wt refers to the content in mass percentage.
  • EC referred to in the following examples refers to ethylene carbonate
  • DMC refers to dimethyl carbonate
  • EMC refers to ethyl methyl carbonate
  • PC refers to propylene carbonate
  • PP propyl propionate
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 1H-imidazole-1-carboxylate-2-propenyl ester and 1wt% methylene disulfonate to the electrolyte solution to prepare the electrolyte solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of allyl 3,5-dimethylpyrazole-1-carboxylate and 1wt% methylene disulfonate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 3-phenylprop-2-en-1-yl 1H-imidazole-1-carboxylate and 1wt% methylene disulfonate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of allyl 2,3-dihydro-1H-pyrrole-1-carboxylate and 1wt% methylene disulfonate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% allyl 1H-pyrrole-1-carboxylate and 1wt% methylene disulfonate to the electrolytic solution to prepare the electrolytic solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1wt% methylene disulfonate to the electrolyte to prepare the electrolyte.
  • EC, PC, and PP were mixed uniformly at a volume ratio of 2:1:5, and 1mol/L LiPF 6 was added to the mixed solution, and then Add 2wt% succinonitrile, 4wt% fluoroethylene carbonate, 0.1wt% 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1wt% methanedisulfonate in the electrolyte Methyl ester to prepare the electrolyte.
  • EC, PC, and PP were mixed uniformly at a volume ratio of 2:1:5, and 1mol/L LiPF 6 was added to the mixed solution, and then Add 2wt% succinonitrile, 4wt% fluoroethylene carbonate, 0.5wt% 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1wt% methanedisulfonate in the electrolyte Methyl ester to prepare the electrolyte.
  • EC, PC, and PP were mixed uniformly at a volume ratio of 2:1:5, and 1mol/L LiPF 6 was added to the mixed solution, and then Add 1wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1wt% methylene disulfonate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 1H-imidazole-1-carboxylate-2-propenyl ester and 1wt% vinyl sulfate to the electrolyte solution to prepare the electrolyte solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of allyl 3,5-dimethylpyrazole-1-carboxylate and 1wt% vinyl sulfate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 3-phenylprop-2-en-1-yl 1H-imidazole-1-carboxylate and 1wt% vinyl sulfate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% allyl 2,3-dihydro-1H-pyrrole-1-carboxylate and 1wt% vinyl sulfate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of allyl 1H-pyrrole-1-carboxylate and 1wt% vinyl sulfate to the electrolytic solution to prepare the electrolytic solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the 0.5 wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1 wt% of vinyl sulfate were respectively added to the electrolyte solution to prepare the electrolyte solution.
  • the electrolytes prepared in the above-mentioned Examples 10 to 16 and the following Comparative Example 8 were respectively tested in a 4.35V lithium cobalt oxide graphite battery for 4 hours at a high temperature of 85°C for capacity retention (constant current/constant voltage at 25°C Charged to 4.35V at 1C under (CC/CV) conditions, and then placed in an oven at 85°C for 4 hours, divided the capacity of 1C discharged to 3.0V after storage by the capacity of 1C discharged to 3.0V after charging under the same conditions before storage ), 300-cycle cycle capacity retention at 45°C (charged at 1C to 4.35V under constant current/constant voltage (CC/CV) conditions at 45°C, then discharged to 3.0V at 1C, and tested the initial capacity, and cycled for 300 cycles according to this method
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution to prepare electrolytic liquid.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 0.5wt% of 1H-imidazole-1-carboxylate-2-propenyl ester to the electrolytic solution to prepare the electrolytic solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the 1wt% methylene disulfonate was added to the electrolytic solution to prepare the electrolytic solution.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the 0.5wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate was added to the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the 0.5 wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate and 1 wt% of 1,3 propane sultone were respectively added to the electrolyte solution to prepare the electrolyte solution.
  • EC, PC, and PP were mixed uniformly at a volume ratio of 2:1:5, and 1mol/L LiPF 6 was added to the mixed solution, and then Add 2wt% of succinonitrile and 4wt% of fluoroethylene carbonate to the electrolyte to prepare the electrolyte.
  • EC, PC, and PP were mixed uniformly at a volume ratio of 2:1:5, and 1mol/L LiPF 6 was added to the mixed solution, and then Add 2wt% of succinonitrile, 4wt% of fluoroethylene carbonate, and 0.5wt% of 2-propyn-1-yl 1H-imidazole-1-carboxylate to the electrolyte to prepare the electrolyte.
  • EC, DMC and EMC were mixed uniformly at a volume ratio of 1:1:1, and 1mol/L LiPF 6 was added to the mixed solution, and then added to the Add 1wt% vinyl sulfate to the electrolytic solution to prepare the electrolytic solution.

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Abstract

本发明涉及一种非水电解液及锂电池，主要解决了非水电解液在高温易分解、高温循环性能差以及倍率性能差的问题。本发明通过添加剂A和添加剂B联合使用产生的协同效应较好地解决了该问题，本申请中的非水电解液及采用此非水电解液的锂电池具有优异的高温性能、循环性能、倍率性能。

Description

一种非水电解液及锂电池 技术领域
本发明涉及一种非水电解液及锂电池。
背景技术
随着手机、平板电脑、智能穿戴以及ETC等新兴消费领域的出现，锂离子电池凭其高能量密度和长循环寿命显现了极大优势。锂离子电池应用的广泛性要求锂离子电池能够适应不同的使用环境，且需要在不同苛刻环境下均能保持良好的性能，更大温度以及更高倍率使用范围成为了锂离子电池发展的重要课题。
电解液作为锂离子电池的血液对锂离子电池的性能影响非常大，为了提高锂离子电池的循环性能，通常会在电解液中加入成膜添加剂，例如在电解液中加入碳酸亚乙烯酯，能够在电池化成时在电池电极表面形成一层较好的膜，阻止反应的进一步进行，从而提升电池的循环性能，然而加入碳酸亚乙烯酯形成的膜在高温下容易被分解，导致电池在高温下无法发挥作用。而为了提高电池的高温性能，会在电解液中加入双草酸硼酸锂等添加剂，双草酸硼酸锂能够在高温下形成较好的膜，但是由于成膜的厚度较大并且膜的电导率比较低会导致电池的内阻过大，从而影响电池容量以及其他性能。
基于此，如何使锂离子电池能够兼顾高温、循环以及倍率性能成为研究的重点。
发明内容
本发明所要解决的技术问题是克服现有技术的不足，提供一种高温、循环及倍率性能均佳的非水电解液。
本发明还提供了一种高温、循环以及倍率性能均佳的锂电池。
为达到上述目的，本发明采用的技术方案如下：
本发明一方面提供一种非水电解液，包括锂盐、有机溶剂和添加剂，所述添加剂包括添加剂A和添加剂B，所述添加剂A的化学结构式如式(1)所示，所述式(1)为
Figure PCTCN2022110794-appb-000001
其中，所述X、所述Y、所述Z分别独立地选自O、S、N、P、
Figure PCTCN2022110794-appb-000002
中的任一种，所述n为正整数，所述R 3选自氢、卤素、烷基、氰基、卤代烷基、卤代烷氧基 中的任一种，所述R 1选自氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基以及卤代烷氧基中的任一种，所述R 2选自烯基、卤代烯基、烯氧基、卤代烯氧基、苯代烯氧基、亚烯基、卤代亚烯基、亚烯氧基、卤代亚烯氧基、炔基、卤代炔基、炔氧基、卤代炔氧基、氰基中的任一种；
所述添加剂B包括第一添加剂B、第二添加剂B以及第三添加剂B中的一种或多种，
所述第一添加剂B的化学结构式如式(2)所示，所述式(2)为
Figure PCTCN2022110794-appb-000003
其中，所述m、所述p分别独立地选自0、1、2中的任一种，所述A、所述B、所述D分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
所述第二添加剂B的化学结构式如式(3)所示，所述式(3)为
Figure PCTCN2022110794-appb-000004
其中，所述a、所述b、所述c、所述d、所述e分别独立地选自0、1、2，所述E、所述G、所述L、所述J分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
所述第三添加剂B的化学结构式如式(4)所示，所述式(4)为
Figure PCTCN2022110794-appb-000005
其中，所述R 4、所述R 5分别独立地选自氢、烷基、卤素、烷氧基中的任一种，所述x选自0、1、2中的任一种。
本发明中的卤素或者卤代时使用的卤为氟、氯、溴、碘中的一种或多种，优选为氟。
优选地，所述式(1)中的所述X、所述Y、所述Z分别独立地选自N或者
Figure PCTCN2022110794-appb-000006
所述n选自1、2、3、4中的任一种，所述R 3为氢或者碳原子数为1～5的烷基。
进一步优选地，所述式(1)中的所述X、所述Y为
Figure PCTCN2022110794-appb-000007
所述Z选自N或者
Figure PCTCN2022110794-appb-000008
所述n选自1或2，所述R 3为氢或者碳原子数为1～3的烷基。
优选地，所述式(1)中的所述R 1为氢或者碳原子数为1～5的烷基。
进一步优选地，所述式(1)中的所述R 1为氢或者碳原子数为1～3的烷基。
优选地，所述式(1)中的所述R 2选自碳原子数为1～5的亚烯氧基、碳原子数为1～5的烯氧基、碳原子数为8～12苯代烯氧基、碳原子数为1～5的炔基、碳原子数为1～5的炔氧基中的任一种。
根据一些优选的实施方式，所述添加剂A包括1H-咪唑-1-羧酸-2-丙烯酯、3,5-二甲基吡唑-1-羧酸烯丙基酯、3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯、烯丙基2,3-二氢-1H-吡咯-1-羧酸酯、烯丙基1H-吡咯-1-羧酸酯、2-丙炔-1-基1H-咪唑-1-羧酸酯、1-咪唑-1-基戊-4-合1-酮中的一种或多种。
进一步优选地，所述添加剂A包括1H-咪唑-1-羧酸-2-丙烯酯、3,5-二甲基吡唑-1-羧酸烯丙基酯、3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯、烯丙基2,3-二氢-1H-吡咯-1-羧酸酯、烯丙基1H-吡咯-1-羧酸酯、2-丙炔-1-基1H-咪唑-1-羧酸酯中的一种或多种。
优选地，所述添加剂A占所述非水电解液总质量的0.01～2％，进一步为0.1～1.5％，更进一步为0.5～1％。
优选地，所述式(2)中的所述A、所述B、所述D分别独立地选自O或者碳原子数为1～3的烷基。
优选地，所述式(3)中的所述E、所述G、所述L、所述J分别独立地选自O或者碳原子数为1～3的烷基。
优选地，所述式(4)中的所述R 4、所述R 5分别独立地选自氢或者碳原子数为1～5的烷基。
根据一些优选的实施方式，所述添加剂B包括硫酸丙烯酯、硫酸乙烯酯、4-甲基硫酸乙烯酯、4-乙基硫酸乙烯酯、4-丙基硫酸乙烯酯、甲烷二磺酸亚甲酯、季戊四醇硫酸酯中的一种或多种。
进一步优选地，所述添加剂B包括硫酸乙烯酯、甲烷二磺酸亚甲酯、季戊四醇硫酸酯中的一种或多种。
优选地，所述添加剂B占所述非水电解液总质量的0.01～5％，进一步为0.1～3％，再进一步为0.5～2％，更进一步为1～1.5％。
根据一些具体的实施方式，所述添加剂还包括丁二腈和/或氟代碳酸乙烯酯。
进一步优选地，所述丁二腈占所述非水电解液总质量的1～3％，更进一步为1.5～2.5％。
进一步优选地，所述氟代碳酸乙烯酯占所述非水电解液总质量的3～5％，更进一步为3.5～4.5％。
优选地，所述有机溶剂为环状酯和/或链状酯，所述环状酯为γ-丁内酯、碳酸乙烯酯、碳酸丙烯酯、氟代碳酸乙烯酯中的一种或几种；所述链状酯为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、氟代丙酸甲酯、氟代丙酸乙酯、氟代乙酸乙酯中的一种或几种。
进一步优选地，所述有机溶剂为环状酯和链状酯的混合，其中，所述环状酯与所述链状酯以体积比为1：(1～2.5)进行混合。
更进一步优选地，所述环状酯与所述链状酯以体积比为1：(1.5～2)进行混合。
优选地，所述锂盐为六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、无水高氯酸锂、二(三氟甲基磺酸酰)亚胺锂、二氟二草酸磷酸锂、二氟磷酸锂、三氟甲基磺酸锂、二氟二草酸磷酸锂、二草酸硼酸锂、单草酸双氟硼酸锂、双氟磺酰亚胺锂中的一种或者几种。
优选地，所述锂盐的浓度为0.6～1.5mol/L，进一步为0.8～1.3mol/L，更进一步为1～1.2mol/L。
本发明的另一方面提供一种锂电池，包括正极、负极和电解液，其中，所述电解液为上述的非水电解液。
优选地，所述正极为钴酸锂正极材料。
进一步优选地，所述负极为石墨材料。
优选地，所述锂电池为4.35V及以上的高压锂电池。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明通过在非水电解液中添加添加剂A和添加剂B，解决了非水电解液在高温下易分解、高温循环性能差以及倍率性能差的问题，本申请中的非水电解液及采用此非水电解液的锂电池具有优异的高温性能、循环性能、倍率性能。
具体实施方式
锂电池具有快速响应、双向调节、高能量、长寿命、配置灵活等优点被广泛应用，随着应用的广泛性也对锂电池的性能提出了更高要求，不仅需要锂电池能够在更大的温度范围内使用，还要求锂电池能够具有良好的循环性能和倍率性能。基于此，本案发明人经长期研究和大量实践，得以提出本发明的技术方案。
本发明的实施例提供了一种非水电解液，包括锂盐、有机溶剂和添加剂。
(1)添加剂
所述添加剂包括添加剂A和添加剂B，所述添加剂A的化学结构式如式(1)所示，所述式(1)为
Figure PCTCN2022110794-appb-000009
其中，所述X、所述Y、所述Z分别独立地选自O、S、N、P、
Figure PCTCN2022110794-appb-000010
中的任一种，所述n为正整数，所述R 3选自氢、卤素、烷基、氰基、卤代烷基、卤代烷氧基中的任一种，所述R 1选自氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基以及卤代烷氧基中的任一种，所述R 2选自烯基、卤代烯基、烯氧基、卤代烯氧基、苯代烯氧基、亚烯基、卤代亚烯基、亚烯氧基、卤代亚烯氧基、炔基、卤代炔基、炔氧基、卤代炔氧基、氰基中的任一种；
所述添加剂B包括第一添加剂B、第二添加剂B以及第三添加剂B中的一种或多种，
所述第一添加剂B的化学结构式如式(2)所示，所述式(2)为
Figure PCTCN2022110794-appb-000011
其中，所述m、所述p分别独立地选自0、1、2中的任一种，所述A、所述B、所述D分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
所述第二添加剂B的化学结构式如式(3)所示，所述式(3)为
Figure PCTCN2022110794-appb-000012
其中，所述a、所述b、所述c、所述d、所述e分别独立地选自0、1、2，所述E、所述G、所述L、所述J分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
所述第三添加剂B的化学结构式如式(4)所示，所述式(4)为
Figure PCTCN2022110794-appb-000013
其中，所述R 4、所述R 5分别独立地选自氢、烷基、卤素、烷氧基中的任一种，所述x选自0、 1、2中的任一种。
本发明通过向非水电解液中添加添加剂A和添加剂B，通过添加剂A和添加剂B之间的协同作用在高温下降低非水电解液分解的同时增加了锂电池的高温循环性能，并且使锂电池的直流阻抗能够基本维持不变。
进一步地，所述式(1)中的所述X、所述Y、所述Z分别独立地选自N或者
Figure PCTCN2022110794-appb-000014
所述n选自1、2、3、4中的任一种，所述R 3为氢或者碳原子数为1～5的烷基。
更进一步地，所述式(1)中的所述X、所述Y为
Figure PCTCN2022110794-appb-000015
所述Z选自N或者
Figure PCTCN2022110794-appb-000016
所述n选自1或2，所述R 3为氢或者碳原子数为1～3的烷基。
进一步地，所述式(1)中的所述R 1为氢或者碳原子数为1～5的烷基。
更进一步地，所述式(1)中的所述R 1为氢或者碳原子数为1～3的烷基。
进一步地，所述式(1)中的所述R 2选自碳原子数为1～5的亚烯氧基、碳原子数为1～5的烯氧基、碳原子数为8～12苯代烯氧基、碳原子数为1～5的炔基、碳原子数为1～5的炔氧基中的任一种。
具体地，所述添加剂A包括1H-咪唑-1-羧酸-2-丙烯酯
Figure PCTCN2022110794-appb-000017
3,5-二甲基吡唑-1-羧酸烯丙基酯
Figure PCTCN2022110794-appb-000018
3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯
Figure PCTCN2022110794-appb-000019
烯丙基2,3-二氢-1H-吡咯-1-羧酸酯
Figure PCTCN2022110794-appb-000020
烯丙基1H-吡 咯-1-羧酸酯
Figure PCTCN2022110794-appb-000021
2-丙炔-1-基1H-咪唑-1-羧酸酯
Figure PCTCN2022110794-appb-000022
1-咪唑-1-基戊-4-合1-酮
Figure PCTCN2022110794-appb-000023
中的一种或多种。
进一步地，所述添加剂A包括1H-咪唑-1-羧酸-2-丙烯酯、3,5-二甲基吡唑-1-羧酸烯丙基酯、3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯、烯丙基2,3-二氢-1H-吡咯-1-羧酸酯、烯丙基1H-吡咯-1-羧酸酯、2-丙炔-1-基1H-咪唑-1-羧酸酯中的一种或多种。
进一步地，所述添加剂A占所述非水电解液总质量的0.01～2％，进一步为0.1～1.5％，更进一步为0.5～1％。本发明中的添加剂A在添加量少、效果佳。
进一步地，所述式(2)中的所述A、所述B、所述D分别独立地选自O或者碳原子数为1～3的烷基。
进一步地，所述式(3)中的所述E、所述G、所述L、所述J分别独立地选自O或者碳原子数为1～3的烷基。
进一步地，所述式(4)中的所述R 4、所述R 5分别独立地选自氢或者碳原子数为1～5的烷基。
具体地，所述添加剂B包括硫酸丙烯酯、硫酸乙烯酯、4-甲基硫酸乙烯酯、4-乙基硫酸乙烯酯、4-丙基硫酸乙烯酯、甲烷二磺酸亚甲酯、季戊四醇硫酸酯中的一种或多种。
进一步地，所述添加剂B包括硫酸乙烯酯、甲烷二磺酸亚甲酯、季戊四醇硫酸酯中的一种或多种。
进一步地，所述添加剂B占所述非水电解液总质量的0.01～5％，进一步为0.1～3％，再进一步为0.5～2％，更进一步为1～1.5％。
在本发明的一些实施例中所述添加剂还包括丁二腈和/或氟代碳酸乙烯酯。
在一些具体的实施方式中，所述丁二腈占所述非水电解液总质量2％。
在一些具体的实施方式中，所述氟代碳酸乙烯酯占所述非水电解液总质量的4％。
(2)有机溶剂
所述有机溶剂为环状酯和/或链状酯，所述环状酯为γ-丁内酯、碳酸乙烯酯、碳酸丙烯酯、氟代碳酸乙烯酯中的一种或几种；所述链状酯为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、 丁酸乙酯、丁酸丙酯、氟代丙酸甲酯、氟代丙酸乙酯、氟代乙酸乙酯中的一种或几种。当然，对于锂电池领域的其他未列举到的有机溶剂也同样适用于本发明的电解液。
进一步地，所述有机溶剂为环状酯和链状酯的混合，其中，所述环状酯与所述链状酯以体积比1：(1～2.5)进行混合。
其中，当所述添加剂包括丁二腈和/或氟代碳酸乙烯酯时，所述环状酯与所述链状酯以体积比1：(1.5～1.8)进行混合；当所述添加剂不包括丁二腈和/或氟代碳酸乙烯酯时，所述环状酯与所述链状酯以体积比1：(1.8～2.5)进行混合。
本发明中的环状酯与链状酯的组合方式可以为在环状酯中任取一种以上的环状酯与在链状酯中任取一种以上的链状酯进行组合，例如，可以为在环状酯中任取两种环状酯与在链状酯中任取一种链状酯进行组合，也可以为在环状酯中任取一种环状酯与在链状酯中任取两种链状酯进行组合。
(3)锂盐
所述锂盐为六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、无水高氯酸锂、二(三氟甲基磺酸酰)亚胺锂、二氟二草酸磷酸锂、二氟磷酸锂、三氟甲基磺酸锂、二氟二草酸磷酸锂、二草酸硼酸锂、单草酸双氟硼酸锂、双氟磺酰亚胺锂中的一种或者几种。除此之外，本发明还可以使用锂电池用电解质中常用的任何锂盐。
在一些具体的实施例中，所述锂盐为六氟磷酸锂。
进一步地，所述锂盐的浓度为0.6～1.5mol/L。
在一些具体的实施例中，所述锂盐的浓度为1mol/L。
本发明的实施例还提供了一种锂电池，包括正极、负极和电解液，其中，所述电解液为上述非水电解液。
进一步地，所述正极为钴酸锂正极材料。
进一步地，所述负极为石墨材料。
进一步地，所述锂电池为4.35V及以上的高压锂电池。
下面结合实施例对本发明作进一步描述。但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整，未注明的实施条件为本行业中的常规条件。本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
在没有特别说明的情况下，wt指质量百分比含量。
下述实施例中涉及的EC指碳酸乙烯酯、DMC指碳酸二甲酯、EMC指碳酸甲乙酯、PC指碳酸丙烯酯、PP指丙酸丙酯。
实施例1
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的1H-咪唑-1-羧酸-2-丙烯酯以及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例2
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的3,5-二甲基吡唑-1-羧酸烯丙基酯及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例3
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例4
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的烯丙基2,3-二氢-1H-吡咯-1-羧酸酯及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例5
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的烯丙基1H-吡咯-1-羧酸酯及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例6
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯及1wt％甲烷二磺酸亚甲酯，制得电解液。
将上述实施例1至实施例6以及下述对比例1至对比例5配制的电解液，分别在4.35V钴酸锂石墨电池中测试85℃高温搁置4小时容量保持率(在25℃的恒定电流/恒定电压(CC/CV) 条件下以1C充电到4.35V，后在85℃的烘箱中搁置4小时，搁置后1C放电至3.0V的容量除以搁置前以同样条件充电后1C放电至3.0V的容量)、45℃300周循环容量保持率(在45℃的恒定电流/恒定电压(CC/CV)条件下以1C充电到4.35V，后1C放电至3.0V，测试初始容量，按此方法循环300周测试循环后的容量，45℃300周循环容量保持率为循环后的容量除以初始容量)、45℃300周循环的电池鼓胀率(循环后电池厚度与循环前电池厚度差值除以循环前电池厚度)和50％SCO、2C10s(即，电池在50％SCO荷电状态下，2C恒电流放电10S的电压差与电流的比值)的DCR，相关实验数据见表1。
实施例7
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、PC和PP以2:1:5的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加2wt％的丁二腈、4wt％的氟代碳酸乙烯酯，0.1wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯以及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例8
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、PC和PP以2:1:5的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加2wt％的丁二腈、4wt％的氟代碳酸乙烯酯，0.5wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯以及1wt％甲烷二磺酸亚甲酯，制得电解液。
实施例9
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、PC和PP以2:1:5的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加1wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯以及1wt％甲烷二磺酸亚甲酯，制得电解液。
将上述实施例7至实施例9以及下述对比例6至对比例7配制的电解液，分别在4.45V钴酸锂石墨电池中测试85℃高温搁置4小时容量保持率(在25℃的恒定电流/恒定电压(CC/CV)条件下以1C充电到4.45V，后在85℃的烘箱中搁置4小时，搁置后1C放电至3.0V的容量除以搁置前以同样条件充电后1C放电至3.0V的容量)、45℃300周循环容量保持率(在45℃的恒定电流/恒定电压(CC/CV)条件下以1C充电到4.45V，后1C放电至3.0V，测试初始容量，按此方法循环300周测试循环后的容量，45℃300周循环容量保持率为循环后的容量除以初始容量)、45℃300周循环的电池鼓胀率(循环后电池厚度与循环前电池厚度差值除以循环 前电池厚度)和50％SCO、2C10s的DCR(即，电池在50％SCO荷电状态下，2C恒电流放电10S的电压差与电流的比值)，相关实验数据见表1。
实施例10
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的1H-咪唑-1-羧酸-2-丙烯酯以及1wt％硫酸乙烯酯，制得电解液。
实施例11
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的3,5-二甲基吡唑-1-羧酸烯丙基酯及1wt％硫酸乙烯酯，制得电解液。
实施例12
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯及1wt％硫酸乙烯酯，制得电解液。
实施例13
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的烯丙基2,3-二氢-1H-吡咯-1-羧酸酯及1wt％硫酸乙烯酯，制得电解液。
实施例14
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的烯丙基1H-吡咯-1-羧酸酯及1wt％硫酸乙烯酯，制得电解液。
实施例15
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯及1wt％硫酸乙烯酯，制得电解液。
实施例16
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的2-丙炔-1-基
1H-咪唑-1-羧酸酯及1wt％季戊四醇硫酸酯，制得电解液。
将上述实施例10至实施例16以及下述对比例8配制的电解液，分别在4.35V钴酸锂石墨电池中测试85℃高温搁置4小时容量保持率(在25℃的恒定电流/恒定电压(CC/CV)条件下以1C充电到4.35V，后在85℃的烘箱中搁置4小时，搁置后1C放电至3.0V的容量除以搁置前以同样条件充电后1C放电至3.0V的容量)、45℃300周循环容量保持率(在45℃的恒定电流/恒定电压(CC/CV)条件下以1C充电到4.35V，后1C放电至3.0V，测试初始容量，按此方法循环300周测试循环后的容量，45℃300周循环容量保持率为循环后的容量除以初始容量)、45℃300周循环的电池鼓胀率(循环后电池厚度与循环前电池厚度差值除以循环前电池厚度)和50％SCO、2C10s的DCR(即，电池在50％SCO荷电状态下，2C恒电流放电10S的电压差与电流的比值)，相关实验数据见表1。
对比例1
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，制得电解液。
对比例2
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的1H-咪唑-1-羧酸-2-丙烯酯，制得电解液。
对比例3
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加1wt％甲烷二磺酸亚甲酯，制得电解液。
对比例4
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯。
对比例5
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加0.5wt％的2-丙炔-1- 基1H-咪唑-1-羧酸酯及1wt％1,3丙烷磺内酯，制得电解液。
对比例6
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、PC和PP以2:1:5的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加2wt％的丁二腈、4wt％的氟代碳酸乙烯酯制得电解液。
对比例7
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、PC和PP以2:1:5的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中分别添加2wt％的丁二腈、4wt％的氟代碳酸乙烯酯，0.5wt％的2-丙炔-1-基1H-咪唑-1-羧酸酯，制得电解液。
对比例8
在充氩气的手套箱中(H 2O含量<10ppm)，将EC、DMC和EMC以1:1:1的体积比混合均匀，在混合溶液中加入1mol/L的LiPF 6，然后向该电解液中添加1wt％硫酸乙烯酯，制得电解液。
表1
Figure PCTCN2022110794-appb-000024
Figure PCTCN2022110794-appb-000025
以上对本发明做了详尽的描述，其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (15)

  1. 一种非水电解液，包括锂盐、有机溶剂和添加剂，其特征在于：所述添加剂包括添加剂A和添加剂B，所述添加剂A的化学结构式如式(1)所示，所述式(1)为
    Figure PCTCN2022110794-appb-100001
    其中，所述X、所述Y、所述Z分别独立地选自O、S、N、P、
    Figure PCTCN2022110794-appb-100002
    中的任一种，所述n为正整数，所述R 3选自氢、卤素、烷基、氰基、卤代烷基、卤代烷氧基中的任一种，所述R 1选自氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基以及卤代烷氧基中的任一种，所述R 2选自烯基、卤代烯基、烯氧基、卤代烯氧基、苯代烯氧基、亚烯基、卤代亚烯基、亚烯氧基、卤代亚烯氧基、炔基、卤代炔基、炔氧基、卤代炔氧基、氰基中的任一种；
    所述添加剂B包括第一添加剂B、第二添加剂B以及第三添加剂B中的一种或多种，
    所述第一添加剂B的化学结构式如式(2)所示，所述式(2)为
    Figure PCTCN2022110794-appb-100003
    其中，所述m、所述p分别独立地选自0、1、2中的任一种，所述A、所述B、所述D分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
    所述第二添加剂B的化学结构式如式(3)所示，所述式(3)为
    Figure PCTCN2022110794-appb-100004
    其中，所述a、所述b、所述c、所述d、所述e分别独立地选自0、1、2中的任一种，所述E、所述G、所述L、所述J分别独立地选自O、S、N、P中的一种或多种构成的基团或者烷基；
    所述第三添加剂B的化学结构式如式(4)所示，所述式(4)为
    Figure PCTCN2022110794-appb-100005
    其中，所述R 4、所述R 5分别独立地选自氢、烷基、卤素、烷氧基中的任一种，所述x选自0、 1、2中的任一种。
  2. 根据权利要求1所述的非水电解液，其特征在于：所述式(1)中的所述X、所述Y、所述Z分别独立地选自N或者
    Figure PCTCN2022110794-appb-100006
    所述n选自1、2、3、4中的任一种，所述R 3为氢或者碳原子数为1～5的烷基。
  3. 根据权利要求2所述的非水电解液，其特征在于：所述式(1)中的所述R 1为氢或者碳原子数为1～5的烷基。
  4. 根据权利要求2所述的非水电解液，其特征在于：所述式(1)中的所述R 2选自碳原子数为1～5的亚烯氧基、碳原子数为1～5的烯氧基、碳原子数为8～12苯代烯氧基、碳原子数为1～5的炔基、碳原子数为1～5的炔氧基中的任一种。
  5. 根据权利要求1所述的非水电解液，其特征在于：所述添加剂A包括1H-咪唑-1-羧酸-2-丙烯酯、3,5-二甲基吡唑-1-羧酸烯丙基酯、3-苯基丙-2-烯-1-基1H-咪唑-1-羧酸酯、烯丙基2,3-二氢-1H-吡咯-1-羧酸酯、烯丙基1H-吡咯-1-羧酸酯、2-丙炔-1-基1H-咪唑-1-羧酸酯、1-咪唑-1-基戊-4-合1-酮中的一种或多种。
  6. 根据权利要求1所述的非水电解液，其特征在于：所述式(2)中的所述A、所述B、所述D分别独立地选自O或者碳原子数为1～3的烷基。
  7. 根据权利要求1所述的非水电解液，其特征在于：所述式(3)中的所述E、所述G、所述L、所述J分别独立地选自O或者碳原子数为1～3的烷基。
  8. 根据权利要求1所述的非水电解液，其特征在于：所述式(4)中的所述R 4、所述R 5分别独立地选自氢或者碳原子数为1～5的烷基。
  9. 根据权利要求1所述的非水电解液，其特征在于：所述添加剂B包括硫酸丙烯酯、硫酸乙烯酯、4-甲基硫酸乙烯酯、4-乙基硫酸乙烯酯、4-丙基硫酸乙烯酯、甲烷二磺酸亚甲酯、季戊四醇硫酸酯中的一种或多种。
  10. 根据权利要求1所述的非水电解液，其特征在于：所述添加剂A占所述非水电解液总质量的0.01～2％；所述添加剂B占所述非水电解液总质量的0.01～5％。
  11. 根据权利要求1所述的非水电解液，其特征在于：所述添加剂还包括丁二腈和/或氟代碳酸乙烯酯。
  12. 根据权利要求1所述的非水电解液，其特征在于：所述有机溶剂为环状酯和/或链状酯，所述环状酯为γ-丁内酯、碳酸乙烯酯、碳酸丙烯酯、氟代碳酸乙烯酯中的一种或几种；所述链状酯为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、丙酸甲酯、丙酸乙酯、丙酸 丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、氟代丙酸甲酯、氟代丙酸乙酯、氟代乙酸乙酯中的一种或几种。
  13. 根据权利要求1所述的非水电解液，其特征在于：所述锂盐为六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、无水高氯酸锂、二(三氟甲基磺酸酰)亚胺锂、二氟二草酸磷酸锂、二氟磷酸锂、三氟甲基磺酸锂、二氟二草酸磷酸锂、二草酸硼酸锂、单草酸双氟硼酸锂、双氟磺酰亚胺锂中的一种或者几种。
  14. 根据权利要求1所述的非水电解液，其特征在于：所述锂盐的浓度为0.6～1.5mol/L。
  15. 一种锂电池，包括正极、负极和电解液，其特征在于：所述电解液为权利要求1至14中任一项所述的非水电解液。
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