CN116462656A - Synthesis method of cyclic sulfate and application of cyclic sulfate in lithium ion battery - Google Patents

Synthesis method of cyclic sulfate and application of cyclic sulfate in lithium ion battery Download PDF

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CN116462656A
CN116462656A CN202310243484.1A CN202310243484A CN116462656A CN 116462656 A CN116462656 A CN 116462656A CN 202310243484 A CN202310243484 A CN 202310243484A CN 116462656 A CN116462656 A CN 116462656A
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cyclic
electrolyte
cyclic sulfate
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halogen
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吴茂祥
闫春凤
潘荧
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/10—Spiro-condensed systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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

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Abstract

The invention provides a synthetic method for preparing cyclic sulfate, which comprises the following steps: dropwise adding hydrogen peroxide into a mixture containing cyclic sulfite, an organic solvent and a solid catalyst for oxidation reaction; the solid catalyst adopts vanadium-based V/SBA-15 molecular sieve. The product obtained by the method has high recovery rate and high purity; the recycled solvent and catalyst can be directly recycled, so that the production cost is saved, the process byproducts are free of high-salt wastewater, the environment is protected, the method is suitable for large-scale production, and the market prospect is wide. The obtained compound can be used as an electrolyte additive, plays a synergistic effect with fluoroethylene carbonate, and is used for improving the rate capability of a lithium ion battery under high voltage and improving the discharge capacity of the lithium battery under 5C heavy current.

Description

Synthesis method of cyclic sulfate and application of cyclic sulfate in lithium ion battery
Technical Field
The invention belongs to the technical field of organic synthesis, in particular to a cyclic sulfate for a lithium ion battery, and particularly relates to a synthesis method of the cyclic sulfate and application of the cyclic sulfate in the lithium ion battery.
Background
The organic cyclic sulfate additive is an important film forming additive, can inhibit the reduction of the initial capacity of the battery, increase the initial discharge capacity, improve the high-low temperature cycle performance, reduce the expansion of the battery after being placed at high temperature, and improve the charge-discharge performance and the cycle times of the battery. While the traditional ethylene sulfate additive has superior performance in batteries, the traditional ethylene sulfate additive has the essential defects of easy water absorption and hydrolysis in air, unstable heat, color change at room temperature, storage temperature of 2-8 ℃ and need of cold chain logistics, which brings a plurality of inconveniences for industrial production, preparation and transportation. It is particularly important to synthesize a sulfate additive that not only has good thermal stability, but also can improve battery performance well. The sulfate compound with multi-ring connection has larger molecular weight and better thermal stability than the traditional sulfate compound, and in addition, the additive can form an SEI layer on the surface of an anode or the surface of a cathode, so that the expansion of a battery after being placed at high temperature is reduced, and the discharge capacity at low temperature is improved.
The production processes of the cyclic sulfate reported at present mainly comprise an acylation method, a sulfonation addition method and an oxidation method. The acylation method has low yield, strong corrosiveness of byproducts, high equipment requirement and environmental pollution, and is not suitable for large-scale preparation (chem. Eur. J.1997,3, 517-522.). Sulfonation is carried out using ethylene oxide (Fr. Dermande,1992,10, jan.,2664274; CN108658928A) or pentaerythritol (CN 114478570A) with sulfur trioxide, these routes all using highly corrosive and highly irritating sulfur trioxide.
The oxidation process is a preparation process commonly used at present. The first method is that sodium hypochlorite is used for oxidizing the cyclic sulfite, the oxidizing property is strong, but the oxygen content is low, a large amount of sodium chloride wastewater is generated as a byproduct, the method is not environment-friendly, a large amount of sodium ions and chloride ions are introduced into the system, and the later purification difficulty of the additive is increased. Furthermore, in this system, noble metals are used as catalysts, which are difficult to recycle, which results in high production costs (can.j.chem.2013, vol.91; CN112694484a; CN114380844 a;). The second is to oxidize sulfite using sodium periodate as an oxidant, sodium periodate is expensive, and also has a problem of difficult recycling, and is not suitable for industrial production (J.chem. Soc., perkin Trans.2001,1,407-414; can.J. chem.2001, vol.79; J.org. Chem.,1998,63,5240-5244).
Besides the synthesis method, the Zhangjia Kong Tai Hua Rong chemical new material Co.Ltd uses titanium-silicon molecular sieve as a catalyst, hydrogen peroxide as an oxidant, and the method is green and environment-friendly (CN 111285884A), but the reaction time is longer, the yield is lower, the reaction system uses two steps of reactions and is carried out in two different solvents, the subsequent solvent separation and recycling are difficult, and the solvent treatment capacity is larger. The solid catalyst used by the conventional city Ji chemical industry Co-Ltd contains active components, active auxiliary agents and oxide carriers, and the production process has the advantages of no waste salt generation, catalyst recovery, low product yield and low economic benefit (CN 111909129A).
Disclosure of Invention
The invention aims to provide a synthesis method for preparing cyclic sulfate, which can solve the problems existing in the existing synthesis method and can be used as an additive in a lithium ion battery.
The technical scheme of the invention is as follows:
a method for preparing cyclic sulfate by oxidizing cyclic sulfite with hydrogen peroxide comprises the following steps:
dropwise adding hydrogen peroxide into a mixture containing cyclic sulfite, an organic solvent and a solid catalyst for oxidation reaction;
the solid catalyst adopts a vanadium-based V/SBA-15 molecular sieve;
the organic solvent is a single organic solvent and is compatible with the cyclic sulfite and the target cyclic sulfate.
According to an embodiment of the present invention, the cyclic sulfite is reacted to obtain a cyclic sulfate as follows:
wherein R is 1 、R 2 The same or different, independently of one another, from hydrogen, halogen, C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 1-12 Alkoxy, halogen substituted C 1-12 Alkyl-or halogen-substituted C 1-12 An alkoxy group;
a, b are identical or different and are independently selected from 1,2 or 3;
m, n, x, y, p and q are identical or different and are independently selected from 0,1,2 or 3.
According to an embodiment of the invention, the halogen atom is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
According to an embodiment of the invention, the reaction is stirred at-5 to 120 ℃ for 0.5 to 24 hours, for example 0.5 to 7 hours.
According to the embodiment of the invention, after the reaction is finished, the solid catalyst can be filtered out, the filtrate is kept stand for layering, and the organic layer is added with MgSO 4 Drying, filtering again, freezing and crystallizing the filtrate, and drying the crystals to directly obtain the finished product of the cyclic sulfate. The solvent (organic layer) and catalyst recovered in the above method can be directly recycled, i.e., used again as the solvent for the above reaction, without limitation of the number of times.
According to embodiments of the present invention, the vanadium-based V/SBA-15 molecular sieve may be referred to the university of l.p.petrochemical, 2013, 33 (1): 1168-1171.
In a preferred embodiment of the present invention, the reaction solvent is one of dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, toluene, benzene, N-dimethylformamide, N-dimethylacetamide, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate.
In a preferred embodiment of the present invention, the oxidation reaction conditions are: the reaction temperature is 0-35 ℃ and the reaction time is 0.5-7 hours.
In a preferred embodiment of the invention, the molar ratio of the cyclic sulfite to hydrogen peroxide in the hydrogen peroxide is 1:1-20, for example 1:1-5.
In a preferred embodiment of the present invention, the mass concentration of the hydrogen peroxide is 25-35%, for example 30-31%.
In a preferred embodiment of the invention, hydrogen peroxide is added into the reaction system in a dropwise manner.
In a preferred embodiment of the invention, the solid catalyst is used in an amount of 0.2 to 80%, for example 1 to 50%, such as 4 to 10% by mass of the cyclic sulfite.
In a preferred embodiment of the present invention, the cyclic sulfite is selected from one of the following including but not limited to:
wherein R is 1 、R 2 、R 3 、R 4 The same or different, independently of one another, from hydrogen, halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, halogen substituted C 1-6 Alkyl-or halogen-substituted C 1-6 An alkoxy group.
The invention also provides an electrolyte containing the cyclic sulfate obtained by the method and application of the electrolyte in a lithium ion battery.
The cyclic sulfate prepared by the invention can be used as an electrolyte additive. The lithium ion battery also comprises a positive electrode material, a negative electrode material and electrolyte; when used as electrolyte additive, the electrolyte additive can also cooperate with fluoroethylene carbonate to improve the ionic conductivity of lithium ion electrolyte and improve the rate capability of lithium ion batteries.
The invention provides an electrolyte comprising a lithium salt, an anhydrous organic solvent and an electrolyte additive, the electrolyte additive being a cyclic sulfate compound and fluoroethylene carbonate (FEC) as described above,
preferably, the cyclic sulfate compound is specifically shown as follows:
wherein R is 1 、R 2 、R 3 、R 4 Independently of one another selected from hydrogen, halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogen substituted C 1-6 Alkyl-or halogen-substituted C 1-6 An alkoxy group.
According to the invention, the cut-off operating voltage of the lithium ion battery is up to 4.5V.
According to the invention, the discharge capacity of the lithium ion battery can reach 165.4mAh/g under the 5C multiplying power.
According to the invention, the cyclic sulfate accounts for 0.05-10 wt% of the total mass of the electrolyte, and the fluoroethylene carbonate accounts for 1-12 wt% of the total mass of the electrolyte.
According to the invention, the organic solvent accounts for 8-85 wt% of the total mass of the electrolyte; the total concentration of the lithium salt in the electrolyte is 0.6-1.3 mol.L -1 。
According to the present invention, the organic solvent is a chain carbonate or a cyclic carbonate, for example, any one or a mixture of more of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylmethyl carbonate (DMC), preferably two or three of the above organic solvents.
According to the invention, the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium perchlorate (LiClO) 4 ) One or more of the following.
According to the present invention, the specific types of the positive electrode active material and the negative electrode active material are not particularly limited.
According to the invention, the positive electrode active material of the lithium ion battery comprises one or more of lithium cobaltate, nickel-manganese binary material, nickel-cobalt-manganese-lithium ternary material, lithium iron phosphate and lithium manganate.
According to the invention, the anode material is lithium metal, graphite carbon material, coke, mesophase carbon microsphere or silicon-based material.
According to the invention, the positive electrode material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 The negative electrode material is a metal lithium sheet, the electrolyte comprises lithium salt, an organic solvent and an additive, and the lithium salt is selected from LiPF 6 The LiPF is 6 Concentration of 1.0 mol.L -1 The organic solvent is selected from EC: EMC: dmc=1:1:1 (mass ratio), defined as base electrolyte; the additive is cyclic sulfate and fluoroethylene carbonate (FEC), wherein the cyclic sulfate accounts for 0.5% of the total mass of the electrolyte, and the FEC accounts for 3% of the total mass of the electrolyte.
The invention has the following advantages and effects:
the method for synthesizing the cyclic sulfate provided by the invention uses the high-efficiency and low-cost V/SBA-15 molecular sieve as a catalyst, and hydrogen peroxide directly oxidizes the cyclic sulfite to obtain the cyclic sulfate, so that high-salt wastewater is not generated, and the production process is environment-friendly; on the other hand, a single solvent is used, the reaction is mild, the steps are simple, and the reaction yield is high; thirdly, the catalyst can be recycled, so that the production cost is reduced, and the catalyst has outstanding advantages.
In addition, the cyclic sulfate prepared by the invention can be used as an additive of lithium battery electrolyte, and can improve the ionic conductivity of the lithium ion electrolyte and improve the rate capability of the lithium ion battery when being used together with fluoroethylene carbonate (FEC) additive.
Definition and description of terms
The term "C 1-12 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms. Preferably "C 1-6 An alkyl group. C (C) 1-6 Alkyl means straight and branched alkyl groups having 1,2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
The term "C 2-12 Alkenyl "is understood to mean a straight-chain or branched monovalent hydrocarbon radical which contains one or more double bonds and has from 2 to 12 carbon atoms, preferably" C 2-6 Alkenyl groups). "C 2-6 Alkenyl "is understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical which contains one or more double bonds and has 2,3, 4, 5, 6 carbon atoms, in particular 2 or 3 carbon atoms (" C 2-3 Alkenyl "), it is understood that where the alkenyl group contains more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl is, for example, vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylpropane1-alkenyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.
The term "C 2-12 Alkynyl "is understood to mean a straight-chain or branched monovalent hydrocarbon radical which contains one or more triple bonds and has from 2 to 12 carbon atoms, preferably" C 2 -C 6 Alkynyl groups. The term "C 2 -C 6 Alkynyl "is understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical which contains one or more triple bonds and has 2,3, 4, 5, 6 carbon atoms, in particular 2 or 3 carbon atoms (" C 2 -C 3 -alkynyl "). The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylpropan-2-ynyl, 2-methylbutan-3-ynyl, 1-methylbutan-2-ynyl, 3-methylbutan-1-ynyl, 1-ethylpropan-2-ynyl 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2-dimethylbbut-3-ynyl, 1, 1-dimethylbut-3-ynyl, 1-dimethylbut-2-ynyl or 3, 3-dimethylbut-1-ynyl. In particular, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.
The term "C 1-12 Alkoxy "is understood to mean-O-C 1-12 Alkyl, wherein C 1-12 Alkyl has the above definition.
The term "halogen"Represents fluorine, chlorine, bromine and/or iodine. Accordingly, the term "halo substituted" refers to fluoro, chloro, bromo and/or iodo. Within the scope of this document, where an atom, residue, group or moiety is halogenated, the atom at the halogenated position may be mono-, di-or polysubstituted with halogen atoms up to full substitution. For example "halogen-substituted C 1-12 Alkoxy "," halogen substituted C 1-12 An alkyl group. Wherein C is 1-12 Alkyl and C 1-12 Alkoxy has the definition as described above.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1: preparation of vanadium-based V/SBA-15 molecular sieve
A certain amount of ammonium metavanadate and deionized water are added into a beaker, a certain amount of citric acid is added after dissolution, and the acid value of the solution is adjusted to pH=3 by hydrochloric acid, so that a transparent solution A is formed. 11g of P123 is weighed and dissolved in 250g of deionized water, after stirring for 5 hours in a water bath at 40 ℃, 24g of tetraethyl orthosilicate TEOS and A solution are added, the solution is again adjusted to pH value of 3 by hydrochloric acid, after stirring for 20 hours, the mixed solution is put into a hydrothermal tank, crystallized for 24 hours at 100 ℃, dried and dried in an oven at 80 ℃ after suction filtration and washing, and fired for 5 hours at 650 ℃ in a muffle furnace, thus obtaining the vanadium-based V/SBA-15 molecular sieve catalyst.
Example 2: preparation of Compound (1)
150g of pentaerythritol sulfite, 350g of acetonitrile and 6.5g of V/SBA-15 molecular sieve are sequentially added into a reaction bottle, stirring is started, 210g of hydrogen peroxide with the mass concentration of 30% is dropwise added into the reaction system after the mixture is fully dissolved, the mixture is dropwise added within 2 hours, and stirring is continued in a normal-temperature water bath for 3 hours after the dropwise addition is completed. After the reaction is finished, filtering and collecting the molecular sieve catalyst, standing filtrate to obtain an organic layer, drying the organic layer by magnesium sulfate, putting the filtered filtrate into a refrigerator, freezing and crystallizing for one night, filtering out crystals, and rotationally evaporating residual solvent and water at 80 ℃ in vacuum to obtain 166.7g of pentaerythritol sulfate with the structural formula (1), wherein the purity is 99.8%, and the yield is 97.5%.
Example 3: preparation of Compound (2)
The preparation method is basically the same as in example 2, except that pentaerythritol sulfite is replaced with ethylene dithionite to obtain 166.6g of compound (2), with purity of 99.6% and yield of 96.5%.
Example 4: preparation of Compound (3)
The preparation process is essentially the same as in example 2, except that pentaerythritol sulfite is replaced byThe cyclic sulfite gave 165.5g of compound (3) with a purity of 99.7% and a yield of 95.1%.
Example 5: repeated synthesis of vinyl dithionate of compound (2) using recovered V/SBA-15 molecular sieve catalyst
The preparation experiment of the compound (2) vinyl dithionate was repeated according to the feeding amount and the process of example 2 using the catalyst recovered in example 3, and the solid catalyst was continuously recovered for recycling, and the results of the experiment were repeated 6 times, and the 6 times are shown in the following table:
the table shows that the used catalyst vanadium-based V/SBA-15 molecular sieve can be directly put into the next reaction system for recycling without any treatment, the catalyst has stable reaction activity, high product conversion rate and high purity, and meanwhile, the use of noble metal catalyst can be reduced, the cost of raw materials is reduced, and the cost is saved in production.
Example 6: preparation of lithium ion Battery containing Compound (1)
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (1) obtained in the example 2 and fluoroethylene carbonate (FEC), wherein the addition amount of the compound (1) is 0.2% of the total mass of the electrolyte, and the addition amount of the fluoroethylene carbonate is 3% of the total mass of the electrolyte, and stirring uniformly to obtain the electrolyte of the example 6.
Preparation of the battery: high nickel ternary material LiNi of positive electrode active material nickel cobalt manganese 0.6 Co 0.2 Mn 0.2 O 2 And (3) fully stirring and uniformly mixing the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone (NMP) system according to a mass ratio of 8:1:1, coating the mixed slurry on an aluminum foil by using an automatic coating machine, putting the coated pole piece into a vacuum oven at 80 ℃ for drying for 10 hours, and drying and rolling to obtain the positive pole piece. The next day, the large pole piece was roll cut into 16mm small discs at room temperature. Vacuumizing the cut small wafer at 80 ℃ for 12 hours, and placing the dried pole piece in a glove box (moisture) filled with argon<1ppm, oxygen content<1 ppm), a diaphragm, an electrolyte, a lithium sheet and a positive and negative electrode shell to form the 2025 type button cell.
The multiplying power experiment testing method comprises the following steps: 0.1C constant current charge to 4.5V,0.1C constant current discharge to 3.0V, cycle 10 week, 0.2C constant current charge to 4.5V,0.2C constant current discharge to 3.0V, cycle 10 week, 0.5C constant current charge to 4.5V,0.5C constant current discharge to 3.0V, cycle 10 week, 1C constant current charge to 4.5V,1C constant current discharge to 3.0V, cycle 10 week, 2C constant current charge to 4.5V,2C constant current discharge to 3.0V, cycle 10 week, 5C constant current charge to 4.5V,5C constant current discharge to 3.0V, cycle 10 week, 0.1C constant current charge to 4.5V,0.1C constant current discharge to 3.0V. The test results are shown in Table 1.
Example 7: preparation of lithium ion Battery containing Compound (2)
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (2) obtained in the example 3 and fluoroethylene carbonate, wherein the addition amount of the compound (2) is 0.5% of the total mass of the electrolyte, and the addition amount of the fluoroethylene carbonate is 3% of the total mass of the electrolyte, and stirring uniformly to obtain the electrolyte of the example 7.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Example 8: preparation of lithium ion Battery containing Compound (3)
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (3) obtained in the example 4 and fluoroethylene carbonate, wherein the addition amount of the compound (3) is 2% of the total mass of the electrolyte, the addition amount of the fluoroethylene carbonate is 3% of the total mass of the electrolyte, and stirring uniformly to obtain the electrolyte of the example 8.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Example 9
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (1), wherein the addition amount of the compound (1) accounts for the total electrolyte of the electrolyteThe electrolyte of example 9 was obtained after stirring uniformly in an amount of 0.2%.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Example 10
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (2), wherein the addition amount of the compound (2) accounts for 0.5% of the total mass of the electrolyte, and uniformly stirring to obtain the electrolyte of the example 10.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Example 11
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then adding the compound (3), wherein the addition amount of the compound (3) is 2% of the total mass of the electrolyte, and uniformly stirring to obtain the electrolyte of the example 11.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Comparative example 1
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organic solvent EC: EMC: dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 Then fluoroethylene carbonate (FEC) is added, the adding amount of the fluoroethylene carbonate is 3 percent of the total mass of the electrolyte, and the electrolyte of the comparative example 1 is obtained after uniform stirring.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Comparative example 2
Preparation of electrolyte: in a glove box filled with argon (moisture)<1ppm, oxygen content<1 ppm), organicSolvent EC, EMC, dmc=1:1:1 (mass ratio), lithium salt LiPF 6 Preparing the mixture into the mixture with the concentration of 1.0mol.L -1 The electrolyte of comparative example 2 was obtained after stirring uniformly.
The preparation and rate test methods of the battery were substantially the same as in example 6. The test results are shown in Table 1.
Table 1 results of the battery test at magnification
As can be seen from table 1, the two additives, namely, cyclic sulfate and fluoroethylene carbonate, are added to the electrolyte simultaneously to exert a synergistic effect for improving the rate capability of the lithium ion battery at high voltage and increasing the discharge capacity of the lithium battery at a large current of 5C. The electrolyte of the comparative example has little effect in enhancing the rate performance of the battery.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The method for preparing the cyclic sulfate by oxidizing the cyclic sulfite with the hydrogen peroxide is characterized by comprising the following steps:
dropwise adding hydrogen peroxide into a mixture containing cyclic sulfite, an organic solvent and a solid catalyst for oxidation reaction;
the solid catalyst adopts a vanadium-based V/SBA-15 molecular sieve;
the organic solvent is a single organic solvent and is compatible with the cyclic sulfite and the target cyclic sulfate.
2. The method according to claim 1, wherein the cyclic sulfite is reacted to obtain the cyclic sulfate by the following reaction process:
wherein R is 1 、R 2 The same or different, independently of one another, from hydrogen, halogen, C 1-12 Alkyl, C 2-12 Alkenyl, C 2-12 Alkynyl, C 1-12 Alkoxy, halogen substituted C 1-12 Alkyl-or halogen-substituted C 1-12 An alkoxy group;
a, b are identical or different and are independently selected from 1,2 or 3;
m, n, x, y, p and q are identical or different and are independently selected from 0,1,2 or 3.
3. The method according to claim 1 or 2, characterized in that the oxidation reaction conditions are: the reaction temperature is 0-35 ℃ and the reaction time is 0.5-7 hours.
4. A process according to any one of claims 1 to 3, wherein the reaction solvent is one of dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, toluene, benzene, N-dimethylformamide, N-dimethylacetamide, dimethyl carbonate, diethyl carbonate, methylethyl carbonate.
5. The method according to any one of claims 1 to 4, wherein the molar ratio of the cyclic sulfite to hydrogen peroxide in the hydrogen peroxide is 1:1 to 20.
6. The method according to any one of claims 1 to 5, wherein after the reaction is completed, the solid catalyst is filtered out, the filtrate is left to stand for delamination, the organic layer is dried, the filtrate is filtered again, the filtrate is frozen for crystallization, and the crystals are dried to directly obtain the finished cyclic sulfate.
7. The method according to any one of claims 1 to 6, wherein hydrogen peroxide is added dropwise to the reaction system.
8. The process according to any one of claims 1 to 7, wherein the solid catalyst is used in an amount of 0.2 to 80% by mass of the cyclic sulfite.
9. The method according to any one of claims 1-8, wherein the cyclic sulfite is selected from one of the following:
wherein R is 1 、R 2 、R 3 、R 4 The same or different, independently of one another, from hydrogen, halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, halogen substituted C 1-6 Alkyl-or halogen-substituted C 1-6 An alkoxy group.
10. An electrolyte comprising a lithium salt, an anhydrous organic solvent and an electrolyte additive, wherein the electrolyte additive is a cyclic sulfate compound prepared by the method of any one of claims 1 to 9 and fluoroethylene carbonate FEC,
CN202310243484.1A 2023-03-14 2023-03-14 Synthesis method of cyclic sulfate and application of cyclic sulfate in lithium ion battery Pending CN116462656A (en)

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