CN113851720B - Non-aqueous electrolyte of lithium ion battery and application thereof - Google Patents

Non-aqueous electrolyte of lithium ion battery and application thereof Download PDF

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CN113851720B
CN113851720B CN202111269928.6A CN202111269928A CN113851720B CN 113851720 B CN113851720 B CN 113851720B CN 202111269928 A CN202111269928 A CN 202111269928A CN 113851720 B CN113851720 B CN 113851720B
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lithium
lithium ion
ion battery
nonaqueous electrolyte
electrolyte solution
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CN113851720A (en
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洪坤光
潘文成
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Tianjin EV Energies Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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

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Abstract

The invention provides a lithium ion battery non-aqueous electrolyte and application thereof. The lithium ion battery non-aqueous electrolyte comprises an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a compound A and other additives. The electrolyte provided by the invention contains the compound A additive, so that a thin and stable interfacial film can be formed on the surfaces of a positive electrode material and a negative electrode material, the film forming impedance is reduced, meanwhile, transition metal ions dissolved out from the positive electrode material can be captured, the deposition of the transition metal ions on the surface of the negative electrode material is prevented from damaging an SEI film, and the SEI film and other additives are synergistically acted, so that the high-temperature storage performance and the cycle life of a lithium ion battery are improved.

Description

Non-aqueous electrolyte of lithium ion battery and application thereof
Technical Field
The invention belongs to the field of batteries, and particularly relates to a lithium ion battery non-aqueous electrolyte and application thereof.
Background
The lithium ion battery has the advantages of high working voltage, high specific energy density, long cycle life, low self-discharge rate, no memory effect, little environmental pollution and the like, and is widely applied to various electronic consumer goods and power battery markets. In order to meet the requirements of high driving range, normal use in high and low temperature environments, rapid charge and discharge, and long cycle life of electric vehicles, it is necessary to develop a lithium ion battery having higher energy density, excellent high and low temperature performance, high power characteristics, and cycle stability. At present, most of lithium ion batteries adopt a non-aqueous electrolyte system which takes lithium hexafluorophosphate as a main lithium salt and a carbonate solvent.
However, the non-aqueous electrolyte system of the lithium ion battery still has many defects, for example, during the charging and discharging process of the battery, side reactions can continuously occur at the interface of the electrode material and the electrolyte, which further causes the swelling of the battery core, increases the internal resistance of the battery, and affects the electrochemical performance of the lithium ion battery. Particularly, when the battery operates at a high temperature, a Solid Electrolyte Interface (SEI) on the negative electrode side is easily decomposed by heat, thereby causing a reductive decomposition reaction of the Electrolyte; meanwhile, transition metal ions on the positive electrode side are extracted and transferred to the negative electrode to damage an SEI film and consume active lithium ions, so that the electrochemical performance of the battery is deteriorated and even the battery is invalid. If the reaction is too violent, the heat can be continuously released, if the heat released by the reaction can not be timely dissipated, the battery core expands and leaks, and even a series of safety problems such as combustion and explosion are caused.
CN111261938A discloses a nonaqueous electrolyte for sodium-ion batteries, which comprises a sodium salt, an additive and an organic solvent. The additive adopts metal chloride with Lewis acidity, but the cycle life of the sodium-ion battery is short and the specific capacity is attenuated continuously. CN106920988A discloses a sodium ion battery electrolyte and a cyclic sulfate additive, wherein the additive is a cyclic organic sulfate additive, and the preparation process is complicated, and the cycle performance and the capacity retention rate are poor.
In view of the above, it is desirable in the art to develop an electrolyte for a lithium ion battery that is capable of not only forming a stable and thin SEI film, but also improving the electrochemical performance of the battery at high temperatures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a lithium ion battery nonaqueous electrolyte and application thereof. The electrolyte provided by the invention contains the compound A additive, so that a thin and stable interfacial film can be formed on the surfaces of a positive electrode material and a negative electrode material, the film forming impedance is reduced, meanwhile, transition metal ions dissolved out from the positive electrode material can be captured, the SEI film is prevented from being damaged by deposition on the surface of the negative electrode material, and the high-temperature storage performance and the cycle life of a lithium ion battery are further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium-ion battery nonaqueous electrolyte comprising an electrolyte, a nonaqueous solvent, and an additive containing a compound a having a structure represented by formula 1:
Figure BDA0003328373250000021
wherein R is 1 、R 2 、R 3 And R 4 Each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkenyl, and substituted or unsubstituted C1-C20, an isocyanate group, a substituted or unsubstituted ether group, a substituted or unsubstituted sulfonyl group, and a substituted or unsubstituted sulfonate group.
The invention provides a lithium ion battery non-aqueous electrolyte, which can form a stable SEI film on the surfaces of a positive electrode material and a negative electrode material by introducing a compound A additive with a diurea structure into the electrolyte, has smaller film forming impedance, can be complexed with transition metal ions removed from the positive electrode material in the battery circulation process, prevents the transition metal ions from being separated out on one side of the negative electrode, and simultaneously has synergistic effect with other additives, thereby improving the high-temperature electrochemical performance of the lithium ion battery.
Preferably, R in said compound A 1 、R 2 、R 3 And R 4 Each independently selected from a fluorine-substituted C1-C20 alkyl group, a fluorine-substituted C1-C20 alkenyl group, a fluorine-substituted C1-C20 alkynyl group, a fluorine-substituted ether group, a fluorine-substituted sulfonyl group or a fluorine-substituted sulfonate group.
Preferably, the compound A is at least one of the following compounds;
Figure BDA0003328373250000031
in the context of the present invention, the compound A may be, for example, the compounds I and II, the compounds III and IV, the compounds V or VI, but is not limited to the species listed, and other species not listed within the scope of the compound A are likewise suitable.
Preferably, the mass percentage of the compound a in the non-aqueous electrolyte solution of the lithium ion battery is 0.05 to 10%, for example, 0.05%,0.5%,1%,2%,5% or 10%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the content of the other additives in the non-aqueous electrolyte solution of the lithium ion battery is 0.05 to 10% by mass, for example, 0.05%,0.5%,1%,2%,5% or 10% by mass, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the other additives in the non-aqueous electrolyte solution of the lithium ion battery include any one or a combination of at least two of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, methylene methane disulfonate, propylene sulfonate, propylene sulfite, ethylene sulfite, propyl phosphoric anhydride, tris (trimethylsilyl) borate, triallyl phosphate, triallyl propyl phosphate, tris (trimethylsilyl) phosphite, maleic anhydride, citraconic anhydride or succinic anhydride, such as vinylene carbonate and vinyl ethylene carbonate, fluoroethylene carbonate and 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate or propylene sulfate, but are not limited to the listed species, and other species not listed within the scope of other additives are also applicable.
Preferably, the electrolyte is a lithium salt.
Preferably, the lithium salt includes any one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium biethanedioate borate, lithium difluorooxalate borate, lithium bistrifluoromethanesulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium difluorooxalate phosphate, such as lithium hexafluorophosphate and lithium tetrafluoroborate, lithium trifluoromethanesulfonate and lithium biethanedioate borate, lithium difluorooxalate borate or lithium bistrifluoromethanesulfonylimide, but is not limited to the listed species, and other species not listed in the lithium salt range are also applicable.
Preferably, the concentration of the lithium salt in the non-aqueous electrolyte solution of the lithium ion battery is 0.5 to 5mol/L, for example, 0.5mol/L,1mol/L,1.5mol/L,2mol/L,2.5mol/L or 5mol/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the non-aqueous solvent includes any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, or propyl butyrate, for example, ethylene carbonate and propylene carbonate, gamma-butyrolactone and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, or propyl butyrate, but is not limited to the listed species, and other species not listed in the non-aqueous solvent are equally applicable.
Preferably, the content of the nonaqueous solvent in the nonaqueous electrolyte solution of the lithium ion battery is 60 to 90% by mass, for example, 60%,65%,70%,75%,85% or 90% by mass, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a second aspect, the invention provides a lithium ion battery, which comprises the lithium ion battery nonaqueous electrolyte solution of the first aspect.
Preferably, the lithium ion battery further comprises a positive plate, a negative plate and a diaphragm.
Preferably, the positive electrode sheet includes a positive electrode collector and a positive electrode active material coated on the positive electrode collector.
Preferably, the negative electrode tab includes a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector.
Preferably, the positive active material includes LiCoO 2 、LiMn 2 O 4 、LiMnO 2 、Li 2 MnO 4 、LiFePO 4 、Li 1+ a Mn 1-x M x O 2 、LiCo 1-x M x O 2 、LiFe 1-x M x PO 4 、LiMn 2-y M y O 4 Or Li 2 Mn 1-x O 4 Any one or combination of at least two of the above, wherein M is at least one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, B, F or Y, and a is more than or equal to 0 and less than or equal to<0.2,0. Ltoreq. X.ltoreq.1, 0. Ltoreq. Y.ltoreq.1, for example LiCoO 2 And LiMn 2 O 4 、LiMnO 2 And Li 2 MnO 4 、LiFePO 4 、Li 1.2 Mn 0.5 Co 0.5 O 2 、LiCo 0.6 Al 0.4 O 2 Or LiFePO 4 But not limited to the listed species, other species not listed within the scope of the positive electrode active material are also applicable.
Preferably, the negative active material includes any one or a combination of at least two of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon oxy compound or silicon carbon alloy, for example, artificial graphite and natural graphite, soft carbon and hard carbon, lithium titanate, lithium, silicon oxy compound or silicon carbon alloy, but is not limited to the listed species, and other species not listed in the scope of negative active material are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a lithium ion battery non-aqueous electrolyte, which is characterized in that a compound A additive with a diurea structure is added into the electrolyte, so that a thin and stable SEI film can be formed on the surfaces of a positive electrode material and a negative electrode material, the electrolyte can be complexed with lithium ions removed from the positive electrode material, the consumption of the lithium ions in the electrolyte is reduced, the SEI film is prevented from being damaged by the lithium ions separated from the negative electrode material, the generated gas is inhibited by the synergistic effect of the electrolyte and other additives, and the high-temperature cycle performance and the rate capability of a lithium ion battery can be improved.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises 5 mass percent of compound ii, 1 mass percent of ethylene sulfate, 2.5 mass percent of vinylene carbonate and 1.5 mass percent of 1, 4-butanesultone additive, the lithium salt comprises lithium bis-fluorosulfonyl imide with a concentration of 2.5mol/L, and the balance is a nonaqueous solvent, and the composition and mass ratio of each solvent in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the electrolyte is prepared in a glove box, wherein the argon content in the glove box is 99.999%, the actual oxygen content is less than 0.1ppm, and the moisture content is less than 0.1ppm. And uniformly mixing the non-aqueous solvent, the additive and the lithium salt according to the proportion to prepare the non-aqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
preparing a positive plate: the lithium nickel cobalt manganese oxide (LiNi) as the anode active material is added 0.7 Co 0.1 Mn 0.2 O 2 ) The conductive agent carbon black (Super-P), the carbon nano tube and the binder polyvinylidene fluoride are dissolved in the solvent N-methyl pyrrolidone according to the mass ratio of 96.5. And then uniformly coating the positive electrode slurry on a current collector aluminum foil, drying at 110 ℃, cold pressing, trimming, cutting into pieces, slitting, drying for 4 hours at 110 ℃ under a vacuum condition, and welding tabs to prepare the positive electrode piece of the lithium ion battery.
Preparing a negative plate: dissolving artificial graphite serving as a negative electrode active material, carbon black serving as a conductive agent (Super-P), carboxymethyl cellulose sodium serving as a thickening agent and styrene butadiene rubber serving as a binder in deionized water according to a mass ratio of 95.8. And then uniformly coating the negative electrode slurry on the front surface and the back surface of the current collector copper foil, drying at 110 ℃, cold pressing, trimming, cutting, splitting, and slitting, drying for 4 hours at 110 ℃ under a vacuum condition, and welding tabs to prepare the negative electrode sheet of the lithium ion battery.
Stacking the positive plate, the lithium battery isolation film and the negative plate in sequence to enable the lithium battery isolation film to be positioned between the positive plate and the negative plate to play a role in isolation, and then winding to obtain a bare cell; and placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried battery, and performing vacuum packaging, standing, formation, aging and other processes to obtain the lithium ion battery.
Example 2
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 0.05% of compound ii, 2.5% of ethylene sulfate, 2.5% of vinylene carbonate and 5% of an additive of 1, 4-butanesultone, and a lithium salt comprises lithium bis (fluorosulfonyl) imide at a concentration of 5mol/L, and the balance is a nonaqueous solvent, and the composition and mass ratio of each solvent in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the lithium ion nonaqueous electrolyte of this example was prepared in the same manner as in example 1, and the composition and ratio of the nonaqueous electrolyte were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 3
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 10% of compound ii, 0.025% of ethylene sulfate and 0.025% of an additive of vinylene carbonate, with respect to 100% of the total mass of the nonaqueous electrolyte, and a lithium salt comprises lithium bis-fluorosulfonylimide with a concentration of 0.5mol/L, and the balance is a nonaqueous solvent, and the nonaqueous solvent comprises the following components in a mass ratio of ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the lithium ion nonaqueous electrolyte of this example was prepared in the same manner as in example 1, and the composition and ratio of the nonaqueous electrolyte were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 4
The present example is different from example 1 in that, instead of adding ethylene sulfate, vinylene carbonate and 1, 4-butane sultone, only 5% by mass of compound ii is added based on 100% by mass of the total mass of the nonaqueous electrolytic solution, the lithium salt includes lithium bis-fluorosulfonyl imide at a concentration of 2.5mol/L, and the balance is a nonaqueous solvent, and the composition and mass ratio of each solvent in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 5
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the total mass of the nonaqueous electrolyte is 100%, the lithium ion nonaqueous electrolyte comprises 1% of compound i, 0.5% of fluoroethylene carbonate, 1% of vinylene carbonate and 1% of vinyl sulfate as additives by mass, lithium salts comprise lithium hexafluorophosphate with the concentration of 1mol/L and lithium bifluorosulfonylimide with the concentration of 0.2mol/L, and the balance is a nonaqueous solvent, and the solvent composition and mass ratio in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 6
The difference between this example and example 5 is that the mass percent of compound i is 0.1% based on 100% of the total mass of the nonaqueous electrolyte, and the amount of the nonaqueous solvent is adjusted to 100% of the total mass of the electrolyte, and the other raw materials, the mixture ratio and the mass percent of each component are the same as those in example 5.
Example 7
The difference between this example and example 5 is that the mass percent of compound i is 5% based on 100% of the total mass of the nonaqueous electrolyte, and the amount of the nonaqueous solvent is adjusted to make the total amount of the electrolyte 100%, and the mass percent of other raw materials, mixture ratios and components are the same as those in example 5.
Example 8
The present example is different from example 5 in that the compound i was contained in an amount of 10% by mass based on 100% by mass of the total amount of the nonaqueous electrolyte, and the amount of the nonaqueous solvent was adjusted to 100% by mass of the total amount of the electrolyte, and the other raw materials, the compounding ratios, and the mass percentages of the components were the same as those in example 5.
Example 9
This example differs from example 5 in that compound i was replaced with compound ii, which was otherwise the same as example 5.
Example 10
This example is different from example 5 in that the compound i was replaced with the compound iii in an amount of 3% by mass based on 100% by mass of the total amount of the nonaqueous electrolytic solution, and the amount of the nonaqueous solvent was adjusted to 100% by mass of the total amount of the electrolytic solution, and the other raw materials, compounding ratios, and the mass% contents of the respective components were the same as in example 5.
Example 11
The difference between the present example and example 5 is that the compound i is replaced by the compound iv based on 100% of the total mass of the nonaqueous electrolytic solution, the mass percentage of the compound iv is 1.5%, the amount of the nonaqueous solvent is adaptively adjusted to make the total amount of the electrolytic solution 100%, and the other raw materials, the mixture ratio and the mass percentage of each component are the same as those in example 5.
Example 12
The difference between the present example and example 5 is that compound v was substituted for compound i based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of compound v was adjusted to 2% by mass, the total amount of the electrolytic solution was adjusted to 100% by mass by adjusting the amount of the nonaqueous solvent, and the other raw materials, the compounding ratios, and the mass percentages of the components were the same as those in example 5.
Example 13
The difference between the present example and example 5 is that the compound i is replaced by the compound vi based on 100% of the total mass of the nonaqueous electrolytic solution, the mass percentage of the compound vi is 0.5%, the amount of the nonaqueous solvent is adaptively adjusted to make the total amount of the electrolytic solution 100%, and the other raw materials, the mixture ratio and the mass percentage of each component are the same as those in example 5.
Example 14
This example is different from example 5 in that the compound i is replaced with the compound v, the lithium ion nonaqueous electrolytic solution includes an additive containing 3% by mass of the compound v and 1% by mass of propylene sultone, the lithium salt includes lithium hexafluorophosphate at a concentration of 0.8mol/L and lithium difluorosulfonimide at a concentration of 0.2mol/L, and the balance is a nonaqueous solvent in which the respective solvent compositions and mass ratios are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 3.
The preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the lithium ion nonaqueous electrolyte of this example was prepared in the same manner as in example 1, and the composition and ratio of the nonaqueous electrolyte were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 15
The present embodiment provides a lithium ion battery nonaqueous electrolyte, where the total mass of the nonaqueous electrolyte is 100%, the lithium ion nonaqueous electrolyte includes, by mass, 0.5% of compound iii, 0.5% of propylene sultone, 0.5% of vinyl sulfate, 0.5% of methylene methanedisulfonate, and 0.3% of propyl phosphoric anhydride as additives, the lithium salt includes lithium hexafluorophosphate having a concentration of 1.1mol/L, 0.1mol/L of lithium bis-fluorosulfonylimide, and 0.05mol/L of lithium difluorophosphate, and the balance is a nonaqueous solvent, and the solvent composition and mass ratio in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 25.
The preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the lithium ion nonaqueous electrolyte of this example was prepared in the same manner as in example 1, and the composition and ratio of the nonaqueous electrolyte were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 16
This example is different from example 15 in that compound v was substituted for compound iii based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of compound v was 2% by mass, the amount of the nonaqueous solvent was adjusted to 100% of the total amount of the electrolytic solution, and the other raw materials, the compounding ratio, and the mass% of each component were the same as those in example 15.
Example 17
This example is different from example 15 in that the compound iii was replaced with the compound vi in a mass percentage of 1% based on 100% of the total mass of the nonaqueous electrolytic solution, and the amount of the nonaqueous solvent was adjusted adaptively so that the total amount of the electrolytic solution is 100%, and the other raw materials, the compounding ratios, and the mass percentages of the respective components were the same as those in example 15.
Example 18
This example differs from example 15 in that compound iii was replaced with compound i, the lithium ion nonaqueous electrolyte solution includes, in mass percentage, 1.5% of compound i, 0.3% of ethylene carbonate, 1.5% of vinyl sulfate, and 0.5% of tris (trimethylsilane) phosphate as additives, based on 100% of the total mass of the nonaqueous electrolyte solution, the lithium salt includes lithium hexafluorophosphate at a concentration of 1.2mol/L, and the balance is a nonaqueous solvent, and the solvent composition and mass ratio in the nonaqueous solvent are ethylene carbonate/ethyl methyl carbonate/diethyl carbonate = 25.
The preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the embodiment is the same as that of the embodiment 1.
Example 19
This example is different from example 15 in that compound I was replaced with compound iv in an amount of 3% by mass based on 100% by mass of the total amount of the nonaqueous electrolytic solution, and the amount of the nonaqueous solvent was adjusted adaptively so that the total amount of the electrolytic solution is 100%, and the other raw materials, compounding ratios, and the mass% of each component were the same as in example 18.
Example 20
This example is different from example 18 in that compound I was replaced with compound ii based on 100% of the total mass of the nonaqueous electrolytic solution, the content of compound ii was 0.5% by mass, the amount of the nonaqueous solvent was adjusted to 100% of the total mass of the electrolytic solution, and the other raw materials, compounding ratios, and the content of each component by mass were the same as in example 18.
Comparative example 1
The comparative example is different from example 5 in that compound i is not added based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of the nonaqueous solvent is adjusted to 100% of the total amount of the electrolytic solution, and the other raw materials, the compounding ratio, and the mass percentages of the components are the same as those of example 5.
Comparative example 2
This comparative example is different from example 14 in that the compound V was not added based on 100% by mass of the total nonaqueous electrolytic solution, and the amount of the nonaqueous solvent was adjusted to 100% by mass of the total electrolytic solution, and other raw materials, compounding ratios, and the content by mass of each component were the same as those of example 14.
Comparative example 3
The comparative example is different from example 15 in that compound iii is not added based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of the nonaqueous solvent is adjusted to 100% of the total amount of the electrolytic solution, and other raw materials, compounding ratios, and mass percentages of the respective components are the same as those in example 15.
Comparative example 4
The comparative example is different from example 20 in that the compound II is not added based on 100% of the total mass of the nonaqueous electrolytic solution, the amount of the nonaqueous solvent is adjusted to 100% of the total amount of the electrolytic solution, and other raw materials, compounding ratios, and mass percentages of the components are the same as those in example 18.
Test conditions
The lithium ion batteries prepared in examples 1 to 20 and comparative examples 1 to 4 were respectively tested for high temperature performance and cycle performance by the following methods:
(1) And (3) testing the cycle performance: the battery was subjected to charge-discharge cycle tests at a rate of 1C in thermostated chambers of 25 ℃ and 45 ℃ respectively, and the capacity retention rate was calculated according to the following formula:
capacity retention = nth discharge capacity/first discharge capacity × 100%.
(2) And (3) testing high-temperature performance: charging the battery to an upper limit voltage at a constant current and a constant voltage at a rate of 1C under a normal temperature state, discharging the battery to a lower limit voltage at a constant current at a rate of 1C, circulating for 3 times in the way, and recording the 3 rd discharge capacity as an initial capacity; and then charging the battery with constant current and constant voltage at a rate of 1C to an upper limit voltage, placing the battery in a thermostat at 55 ℃ for 30 days, taking out the battery, discharging the battery with constant current at a rate of 1C to a lower limit voltage at normal temperature, recording as a retention capacity, and calculating a capacity retention rate according to the following formula:
capacity retention = holding capacity/initial capacity × 100%
Charging the battery with constant current and constant voltage to an upper limit voltage at a rate of 1C, discharging the battery with constant current to a lower limit voltage at the rate of 1C, circulating for 3 times, recording the 3 rd discharge capacity as a recovery capacity, and calculating the capacity recovery rate according to the following formula:
capacity recovery = recovered capacity/original capacity × 100%.
The results of the test are shown in table 1:
table 1:
Figure BDA0003328373250000151
as can be seen from table 1, compared with comparative examples 1 to 4, in examples 1 to 20, due to the addition of the compound a additive having a diurea structure, the capacity retention rate of the lithium ion battery after cycling at 25 ℃ and 45 ℃ is as high as more than 80%, and the capacity retention rate and the capacity recovery rate of the lithium ion battery at high temperature storage at 55 ℃ are significantly improved, and are not lower than 90%; the lithium ion battery prepared without the compound A additive has the capacity retention rate of less than 60% in circulation at 25 ℃ and 45 ℃, and the capacity retention rate and the capacity recovery rate of high-temperature storage of the lithium ion battery at 55 ℃ are less than 90%, so that the nonaqueous electrolyte provided by the invention is further proved to greatly improve the high-temperature storage performance and the circulation performance of the battery.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (16)

1. A lithium ion battery nonaqueous electrolyte solution is characterized by comprising an electrolyte, a nonaqueous solvent and an additive, wherein the additive comprises a compound A with a structure shown in a formula 1 and other additives:
Figure FDA0003911908950000011
wherein R is 1 、R 2 、R 3 And R 4 Each independently selected from the group consisting of a fluorine substituted or unsubstituted C1-C20 alkyl group, a fluorine substituted or unsubstituted C1-C20 alkenyl group, a fluorine substituted or unsubstituted C1-C20 alkynyl group, an isocyanate group, a fluorine substituted or unsubstituted ether group, a fluorine substituted or unsubstituted sulfonyl group, and a fluorine substituted or unsubstituted sulfonate group.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the compound a is at least one of the following compounds;
Figure FDA0003911908950000012
Figure FDA0003911908950000021
3. the nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the mass percentage of compound a in the nonaqueous electrolyte solution for lithium ion batteries is 0.05 to 10%.
4. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the content of other additives in the nonaqueous electrolyte solution for lithium ion batteries is 0.05 to 10% by mass.
5. The nonaqueous electrolyte solution for lithium-ion batteries according to claim 1, wherein other additives in the nonaqueous electrolyte solution for lithium-ion batteries include any one of vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, vinyl sulfite, propylene sulfite, methylene methane disulfonate, propylene sultone, propylene sulfite, vinyl sulfite, propyl phosphoric anhydride, tris (trimethylsilane) borate, triallyl phosphate, tripenylpropargyl phosphate, tris (trimethylsilane) phosphite, maleic anhydride, citraconic anhydride, or succinic anhydride, or a combination of at least two thereof.
6. The nonaqueous electrolyte solution for lithium-ion batteries according to claim 1, wherein the electrolyte is a lithium salt.
7. The nonaqueous electrolyte solution for lithium-ion batteries according to claim 6, wherein the lithium salt comprises any one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bistrifluoromethanesulfonylimide, lithium difluorosulfonimide, lithium difluorophosphate or lithium difluorooxalato phosphate, or a combination of at least two thereof.
8. The nonaqueous electrolyte solution for lithium ion batteries according to claim 6, wherein the concentration of the lithium salt in the nonaqueous electrolyte solution for lithium ion batteries is 0.5 to 5mol/L.
9. The nonaqueous electrolyte for a lithium ion battery according to claim 1, wherein the nonaqueous solvent comprises any one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ -butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, or propyl butyrate, or a combination of at least two thereof.
10. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the nonaqueous solvent is contained in the nonaqueous electrolyte solution for lithium ion batteries in an amount of 60 to 90% by mass.
11. A lithium ion battery comprising the lithium ion battery nonaqueous electrolyte solution according to any one of claims 1 to 10.
12. The lithium ion battery of claim 11, further comprising a positive plate, a negative plate, and a separator.
13. The lithium ion battery of claim 12, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector.
14. The lithium ion battery according to claim 12, wherein the negative electrode tab comprises a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector.
15. The li-ion battery of claim 13, wherein the positive active material comprises LiCoO 2 、LiMn 2 O 4 、LiMnO 2 、Li 2 MnO 4 、LiFePO 4 、Li 1+a Mn 1-x M x O 2 、LiCo 1-x M x O 2 、LiFe 1-x M x PO 4 、LiMn 2-y M y O 4 Or Li 2 Mn 1-x O 4 Any one or combination of at least two of the above, wherein M is at least one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, B, F or Y, and a is more than or equal to 0<0.2，0≤x≤1，0≤y≤1。
16. The lithium ion battery of claim 14, wherein the negative active material comprises any one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon oxy-compound, or silicon carbon alloy, or a combination of at least two thereof.
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