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CN115528309A - Organic electrolyte and lithium ion secondary battery containing the same - Google Patents

Organic electrolyte and lithium ion secondary battery containing the same Download PDF

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Publication number
CN115528309A
CN115528309A CN202211378131.4A CN202211378131A CN115528309A CN 115528309 A CN115528309 A CN 115528309A CN 202211378131 A CN202211378131 A CN 202211378131A CN 115528309 A CN115528309 A CN 115528309A
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compound
lithium
formula
carbonate
organic electrolyte
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佘倩文
李帅龙
玉朝琛
周立
谢添
丁友停
高远鹏
孙文坡
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Jiujiang Tinci Advanced Materials 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
    • 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

Disclosed are an organic electrolyte and a lithium ion secondary battery comprising the same, the organic electrolyte including a nitrile compound and a bicyclic sulfate compound. The organic electrolyte provided by the application is beneficial to improving the cycle life characteristic, the high-temperature storage stability and the rate capability of the lithium ion battery.

Description

Organic electrolyte and lithium ion secondary battery containing the same
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to an organic electrolyte and a lithium ion secondary battery containing the same.
Background
With the rapid iterative upgrade of electronic information technology and consumer electronic devices, the trend of lightweight, light and thin consumer electronic devices is increasingly evident, and lithium ion batteries are the most direct source of energy required by electronic devices, and the requirements for battery performance are continuously increased, and the lithium ion batteries are required to have higher energy density, that is, to provide more energy on the premise of occupying smaller space. Meanwhile, in order to reduce the charging waiting time of a user, the lithium ion battery is required to be rapidly charged, and the lithium ion battery is correspondingly required to have good multiplying power charging and discharging performance.
Therefore, for the lithium ion battery, the current greatest challenge is to improve the volumetric energy density and rate capability of the battery, and simultaneously ensure that the battery can meet the long-term charge and discharge capacity. The most important components of the lithium ion battery are a positive electrode material, a negative electrode material and electrolyte, the electrolyte consists of a solvent, a solute and a functional additive, and is used as the most important components of the lithium ion battery, so that the components of the electrolyte are improved, and the volume energy density and the rate capability of the battery are improved.
Disclosure of Invention
In view of the above, the present application is directed to an organic electrolyte and a lithium ion secondary battery including the same.
In order to achieve the above purpose, the present application mainly provides the following technical solutions:
in a first aspect, the present application provides an organic electrolytic solution comprising:
nitrile compounds, and
a bicyclic sulfate compound having a structure represented by formula 1;
Figure BDA0003927239680000021
in the formula 1, R 1 、R 2 、R 4 、R 5 Each independently selected from a single bond, an alkane or a halogenated alkane, R 3 One selected from the following structures:
Figure BDA0003927239680000022
wherein n is an integer of 0 to 6;
the nitrile compound is selected from one or more of mononitrile compound, dinitrile compound, trinitrile compound and tetranitrile compound.
The electrolyte contains a nitrile compound and a bicyclic sulfate compound with a structure shown in formula 1, and the two substances have a synergistic effect when applied to an organic electrolyte, and are specifically shown in the following steps: the composite modified SEI film is more stable to form on a negative electrode interface through combination or adsorption, direct contact between an organic solvent and the negative electrode interface is effectively reduced, the reversibility of lithium ion insertion/extraction is improved, meanwhile, a nitrile compound and transition metal on a positive electrode interface are subjected to a complex reaction, co dissolution in a positive electrode material is effectively reduced, the effect of protecting the positive electrode interface is achieved, and the cycle life, the high-temperature storage stability and the rate capability of a battery are improved.
As a preferred embodiment of the present application, the bicyclic sulfate compound is selected from one or more of the following compounds in admixture:
Figure BDA0003927239680000031
as a preferred embodiment of the present application, the mononitrile compound is selected from any one or more mixtures of compounds having the structure shown in formula 2:
R 6 -CN is represented by the formula 2,
in the formula 2, R6 is selected from C 1～10 Alkenyl or haloalkenyl, C 1～10 Alkynyl or haloalkynyl of C 1～10 Alkoxy or haloalkoxy of C 1～10 Aryl or halogenated aryl of (a);
as a more preferred embodiment of the present invention, the mononitrile compound is selected from acetonitrile, p-methylbenzonitrile, acrylonitrile, crotononitrile, and 3- (trimethylsiloxy) propionitrile.
As a preferred embodiment of the present application, the dinitrile compound is selected from any one or more mixtures of structural compounds represented by formula 3:
NC-R 7 -CN is represented by the formula 3,
in the formula 3, R 7 Is selected from C 1～10 Alkylene or haloalkylene of, C 1～10 Alkenylene or haloalkenylene of (A), C 1～10 Alkynyl or haloalkynyl of C 1～10 Alkylene oxide or haloalkylene oxide of (a);
as a more preferred embodiment herein, the dinitrile compound is selected from the group consisting of malononitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonadinitrile, sebaconitrile, 2-methylsuccinonitrile, tetramethylsuccinonitrile, 2-methylglutaronitrile, 2-methyleneglutaronitrile, ethoxymethylenemalononitrile, 3, 5-dioxa-pimelinonitrile, ethylene glycol bis (propionitrile) ether, in any combination or mixtures thereof.
As a preferred embodiment of the present application, the nitrile compound is selected from any one or more compounds having a structure represented by formula 4:
Figure BDA0003927239680000041
in the formula 4, R 8 Is selected from C 1～10 Alkylene or haloalkylene of, C 1～10 Alkenylene or haloalkenylene of (A), C 1～10 Alkynyl or haloalkynyl of (A), C 1～10 Alkylene oxide or haloalkylene oxide of (a);
as a more preferred embodiment of the present invention, the trinitrile compound is selected from any one or more of methane-tricitrile, 1,3, 6-hexane-tricitrile, 1,2, 3-tris (2-cyanato) propane, ethylene-1, 2-tricitrile, 1,2, 3-propanetricitrile, and 1,3, 5-pentane-tricitrile.
As a preferable embodiment of the present application, the tetranitrile compound is selected from any one or more mixtures of structural compounds represented by formula 5:
Figure BDA0003927239680000042
in the formula 5, R 9 、R 10 Each independently selected from C 1～10 Alkylene or haloalkylene of, C 1～10 Alkenylene or haloalkenylene of (1), C 1～10 Alkynyl or haloalkynyl of C 1～10 Alkylene oxide or haloalkylene oxide of (a);
as a more preferred embodiment of the present invention, the tetranitrile compound is selected from any one or more of tetracyanoethylene, 1,2, 3-propane-tetracarbonitrile, methane-tetracarbonitrile, 1, 3-propane-tetracarbonitrile, and 1, 2-ethane-tetracarbonitrile.
In a preferred embodiment of the present invention, the content of the bicyclic sulfate compound is 0.3 to 6%; the content of the nitrile compound is 1% to 8%, more preferably 1% to 6%, and preferably 1% to 4%, based on the total mass of the organic electrolyte. When the addition amount of nitrile is more than 8%, the effect of improving high-temperature characteristics is weakened, and the normal-temperature cycle and rate characteristics are poor.
Specifically, the organic electrolytic solution of the present application further includes a conventionally added nonaqueous solvent, a lithium salt, and an additive.
As a preferred embodiment of the present application, the non-aqueous solvent is selected from any one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), dipropyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl Acetate (EA), propyl Acetate (PA), butyl acetate, methyl propionate, ethyl Propionate (EP), propyl Propionate (PP), butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, ethylene glycol dimethyl ether (DME), triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-Dioxypentacyclic (DOL), 1, 4-Dioxane (DOX), sulfolane, tetrahydrofuran (THF), 2-methyltetrahydrofuran, difluorovinyl carbonate (DFEC), dimethyl fluorocarbonate, methyl ethylfluorocarbonate, methyl difluoroacetate, and ethyl difluoroacetate.
The content of the non-aqueous solvent is 55 to 80%, preferably 58 to 78%, based on the total mass of the electrolyte.
As a preferred embodiment of the present application, the lithium salt is selected from any one or a mixture of more of lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium perchlorate (LiClO 4), lithium hexafluoroarsenate (LiAsF 6), lithium difluorophosphate (LiPO 2F 2), lithium 4, 5-dicyano-2-trifluoromethylimidazolium (LiTDI), lithium bis (oxalato) borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium tris (oxalato) phosphate (LiTOP), lithium tetrafluorooxalato phosphate (LiTFOP), lithium difluorooxalato phosphate (LiODFP), lithium bis (fluorosulfonyl) imide (LiFSI), and lithium bistrifluoromethanesulfonylimide (LiTFSI).
The content of the lithium salt is 12-18% based on the total mass of the electrolyte.
As a preferred embodiment of the present application, the additive is selected from any one or more of Vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1,3- (1-Propene) Sultone (PST), fluoromethyl vinyl carbonate, dimethyl sulfate (DMS), vinyl sulfate (DTD), vinyl methyl sulfate, propylene sulfate (TMS), vinyl sulfite, succinic anhydride, biphenyl, diphenyl ether, toluene, xylene, cyclohexylbenzene, fluorobenzene, p-fluorotoluene, p-fluoroanisole, tert-butylbenzene, tert-amylbenzene, methylene methanedisulfonate, ethylene glycol bis (propionitrile) ether, hexamethyldisilazane, heptamethyldisilazane, dimethyl methylphosphonate, diethyl ethylphosphonate, trimethyl phosphate, triethyl phosphate, triphenyl phosphite, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate, and dimethyl sulfoxide.
The content of the additive is 4-10% based on the total mass of the electrolyte.
In the present application, the amounts of the components of the electrolyte can be adjusted according to the above definitions, for example:
the bicyclic sulfate compound may be used in an amount of 0.3%, 0.35%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 2%, 2.5%, 3%, 3.9%, 4%, 4.2%, 5%, 5.5%, 5.6%, 5.8%, 6%, etc.
The nitrile compound may be used in an amount of 1%, 1.5%, 1.8%, 2%, 2.1%, 2.3%, 3%, 3.8%, 4%, 4.6%, 5%, 5.4%, 6%, 6.3%, 6.5%, 7%, 7.8%, 8%, etc.
The amount of lithium salt may be 12%, 12.5%, 13%, 13.5%, 14%, 14.6%, 15%, 16%, 17%, 18%, etc.
The non-aqueous solvent may be used in an amount of 55%, 55.4%, 56%, 56.6%, 57%, 57.2%, 58%, 59%, 59.5%, 60%, 60.3%, 61%, 62%, 62.8%, 62.33%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, etc.
The additives may be used in amounts of 4%, 4.8%, 5%, 5.1%, 5.3%, 5.5%, 6%, 6.9%, 7%, 7.2%, 7.3%, 8%, 8.6%, 8.8%, 9%, 9.5%, 9.7%, 10%, etc.
In a third aspect, the present application also provides a lithium ion secondary battery comprising:
the anode is a positive electrode, and the cathode is a cathode,
a negative electrode, a positive electrode and a negative electrode,
a separator, and
the organic electrolytic solution according to the first aspect.
Based on the description of the first aspect, by adding the electrolyte solution of the first aspect to a lithium ion secondary battery, the cycle life, high-temperature storage stability, and rate capability of the lithium ion secondary battery are better.
In some embodiments of the present application, the positive electrode material may be selected from lithium cobaltate, lithium manganate, lithium nickel cobalt manganese ternary material, lithium nickel manganese, or lithium rich manganese-based material.
In some embodiments of the present application, the negative electrode material may be selected from graphite, hard carbon, soft carbon, mesocarbon microbeads, silicon-based negative electrode materials, or lithium-containing metal composite oxide materials.
In some embodiments of the present application, the separator may be selected from a polyethylene separator or a PE-coated ceramic separator.
The positive electrode and the negative electrode of the lithium ion secondary battery can be prepared by adopting a conventional method in the field, and the lithium ion secondary battery can be assembled by adopting the conventional method.
For example: and conventionally assembling the cut positive pole piece, negative pole piece and diaphragm to obtain the lithium ion secondary battery.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the application applies the dicyclic sulfate compound containing the nitrile compound and the structure shown in the formula 1 in the organic electrolyte, and the dicyclic sulfate compound and the nitrile compound have a synergistic effect, which is shown in the following concrete steps: the composite modified SEI film is more stable to form on a negative electrode interface through combination or adsorption, direct contact between an organic solvent and the negative electrode interface is effectively reduced, the reversibility of lithium ion insertion/extraction is improved, meanwhile, a nitrile compound and transition metal on a positive electrode interface are subjected to a complex reaction, co dissolution in a positive electrode material is effectively reduced, the effect of protecting the positive electrode interface is achieved, and the cycle life, the high-temperature storage stability and the rate capability of a battery are improved.
Detailed Description
The technical solution of the present application is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are those conventional in the art.
Examples
Preparing a lithium ion soft package battery:
and determining the coating surface density according to the capacity design of the battery and the capacities of the anode and cathode materials. The positive active material is lithium cobaltate material purchased from tungsten of mansion; the negative active material is artificial graphite purchased from Shenzhen fenofibrate; the diaphragm is a PE coating ceramic diaphragm which is purchased from a star source material.
The preparation steps of the anode are as follows:
mixing lithium cobaltate, conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 96.8.
The preparation steps of the cathode are as follows:
mixing graphite, conductive carbon black, binder styrene butadiene rubber and carboxymethyl cellulose according to a mass ratio of 95.5; and (4) sequentially stacking the prepared positive plate, the diaphragm and the negative plate, and winding to obtain the bare cell.
The electrolyte is prepared by the following steps:
mixing Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) according to a mass ratio of 25.
And placing the bare cell in an aluminum-plastic film outer package, injecting the prepared electrolyte into the dried battery, packaging, standing, forming and grading to finish the preparation of the lithium ion battery.
The electrolyte formulations used in examples 1-11 and comparative examples 1-5 have the additive amounts shown in table 1:
table 1: examples and comparative examples electrolyte additives types and amounts
Figure BDA0003927239680000091
And (3) testing the performance of the lithium ion battery:
the examples 1-11 and comparative examples 1-5 were tested for cell performance by the following methods:
25 ℃ 2C/1C cycle test: the battery is placed in an environment with the temperature of 25 ℃, the battery is charged to 4.48V by a constant current of 1C and charged to a cut-off current of 0.05V by a constant voltage of 4.48V, the battery is placed for 5 minutes, then the battery is subjected to 1C constant current discharge to 3.0V, and the discharge capacity is marked as C 0 . Charging to 4.48V with 2C constant current, charging to 0.05C with 4.48V constant voltage, standing for 5 min, discharging to 3.0V with 1C constant current cell, standing for 5 min, as a charge-discharge cycle, repeating the charge-discharge process for 300 weeks to obtain 300 week discharge capacity C 300 Capacity retention ratio = C 300 /C 0 *100％。
45 ℃ 2C/1C cycle test: the battery is placed in an environment with the temperature of 25 ℃, the battery is charged to 4.48V by a constant current of 1C and charged to a cut-off current of 0.05V by a constant voltage of 4.48V, the battery is placed for 5 minutes, then the battery is subjected to 1C constant current discharge to 3.0V, and the discharge capacity is marked as C 0 . Placing the battery in an explosion-proof oven at 45 deg.C, charging to 4.48V at 2C constant current, charging to 0.05C at constant voltage of 4.48V to cut-off current, standing for 5 min, discharging to 3.0V at 1C constant current, standing for 5 min, and repeating the steps for 200 weeks to obtain 200 week discharge capacity C 200 Capacity retention ratio = C 200 /C 0 *100％。
And (3) testing the retention rate of the storage capacity at 85 ℃ for 6h, the capacity recovery rate and the thickness expansion rate: charging to 4.48V at 25 deg.C under 1C constant current, charging at constant voltage of 4.48V to 0.05C at cutoff current, standing for 5 min, and discharging at 1C constant current 0 And the thickness of the battery is denoted as D 0 Then the battery is placed in an explosion-proof oven at 85 ℃, and after 6 hours of storage, the thickness D of the battery is tested in the oven 1 Then, the cell was taken out and cooled to room temperature, and the discharge retention capacity C of 1C discharge to 3.0V was tested 2 Then repeating the charging and discharging steps for 3 weeks, and recording the 3 rd week discharge capacity C of the battery 3 Thickness expansion ratio = (D) 1 -D 0 )/D 0 *100% capacity retention = C 2 /C 0 *100% capacity recovery = C 3 /C 0 *100％。
And (3) rate charging test: the cell is placed in an environment with the temperature of 25 ℃, the cell is charged to 4.48V by a constant current of 1C and charged to a cut-off current of 0.05V by a constant voltage of 4.48V, the cell is placed for 5 minutes, then the cell is discharged to 3.0V by a constant current of 1C, and the discharge capacity is marked as C 0 . Charging to 4.48V at constant multiplying power, charging at constant voltage until the current is reduced to 0.05C, standing for 5 minutes, then discharging to 3.0V at constant current at 1C, standing for 5 minutes, which is a charging and discharging cycle, repeating the charging and discharging process steps for 3 weeks, sequentially performing multiplying power charging tests of 0.5C, 1C, 2C, 3C and 4C on the battery, and recording the capacity of the constant current section of the last cycle of 4C multiplying power as C 4 4C constant current rush-in ratio = C 4 /C 0 *100％。
And (3) rate discharge test: the cell is placed in an environment with the temperature of 25 ℃, the cell is charged to 4.48V by a constant current of 1C and charged to a cut-off current of 0.05V by a constant voltage of 4.48V, the cell is placed for 5 minutes, then the cell is discharged to 3.0V by a constant current of 1C, and the discharge capacity is marked as C 0 . Charging to 4.48V at 1C constant current, charging at constant voltage until the current is reduced to 0.05C, standing for 5 minutes, then discharging to 3.0V at constant rate constant current, standing for 5 minutes, which is a charge-discharge cycle, repeating the charge-discharge process step for 3 weeks, sequentially performing rate discharge tests of 0.5C, 1C, 2C, 3C and 4C on the battery, and recording the discharge capacity of the battery at 4C rate in 3 weeks as C 5 Retention ratio of 4C discharge capacity = C 5 /C 0 *100％。
After the electrolyte in the above embodiment is prepared into a lithium ion battery, the normal temperature cycle performance, the high temperature storage performance and the rate performance of the lithium ion battery are tested, and the results are shown in table 2:
table 2: lithium ion battery performance test results
Figure BDA0003927239680000101
Figure BDA0003927239680000111
And (3) analyzing an experimental result:
1. comparing comparative examples 1-3 with examples 1-3 and examples 9-11, it can be seen that when the dicyclic sulfate compound or nitrile compound or dicyclic sulfate compound shown in formula 1 is used alone, the addition amount is greater than 6%, the normal temperature cycle performance, high temperature stability and rate capability of the lithium ion battery are poor, and the gas yield of the battery after high temperature storage is high.
2. Comparing example 3 with comparative example 3, when succinonitrile is used as the nitrile compound, the rate capability of comparative example 3 is poor because adiponitrile has a longer carbon chain and a stronger complexing reaction with the transition metal of the positive interface, which is helpful for forming a more elastic and stable positive interface protective film, thereby significantly improving the normal temperature cycle performance, the high temperature stability and the rate capability
3. By comparing examples 1 to 5 and comparative examples 4 to 5, it is understood that increasing the amount of nitrile compound added has an effect of improving high temperature cycle and high temperature storage, suppressing gas generation in high temperature storage batteries, and that the improvement of nitrile compound over dinitrile compound in high temperature cycle is more significant. However, when the amount of nitrile added is greater than 8%, the effect of improving the high-temperature characteristics is reduced, and the normal-temperature cycle and rate characteristics are deteriorated.
Although the embodiments have been described, once they learn of the basic inventive concept, those skilled in the art can make further changes and modifications to these embodiments, so that these embodiments are merely examples of the present application and do not limit the scope of the claims of the present application, and all the modifications of the equivalent structures or equivalent processes that can be made by the content of the present specification or that can be directly or indirectly applied to other related fields are also included in the scope of the present application.

Claims (10)

1. An organic electrolytic solution, characterized in that it comprises:
nitrile compounds, and
a bicyclic sulfate compound having a structure represented by formula 1;
Figure FDA0003927239670000011
in the formula 1, R 1 、R 2 、R 4 、R 5 Each independently selected from the group consisting of a single bond, an alkane, and a haloalkane, R 3 One selected from the following structures:
Figure FDA0003927239670000012
wherein n is an integer of 0 to 6;
the nitrile compound is selected from one or more of mononitrile compound, dinitrile compound, trinitrile compound and tetranitrile compound.
2. The organic electrolyte of claim 1, wherein the bicyclic sulfate compound is selected from one or more of the following compounds in admixture:
Figure FDA0003927239670000013
Figure FDA0003927239670000021
3. the organic electrolyte as claimed in claim 1, wherein the mononitrile compound is selected from any one or more compounds of formula 2:
R 6 -CN is represented by the formula 2,
in the formula 2, R6 is selected from C 1～10 Alkenyl or haloalkenyl, C 1～10 Alkynyl or haloalkynyl of (A), C 1～10 Alkoxy or haloalkoxy of C 1～10 Aryl or halogenated aryl of (a);
preferably, the mononitrile compound is selected from acetonitrile, p-methylbenzonitrile, acrylonitrile, crotononitrile, 3- (trimethylsiloxy) propionitrile, or a mixture thereof.
4. The organic electrolyte as claimed in claim 1, wherein the dinitrile compound is selected from any one or more mixtures of structural compounds represented by formula 3:
NC-R 7 -CN is represented by the formula 3,
in the formula 3, R 7 Is selected from C 1～10 Alkylene or haloalkylene of, C 1～10 Alkenylene or haloalkenylene of (1), C 1～10 Alkynyl or haloalkynyl of (A), C 1～10 Or haloalkyleneoxy;
preferably, the dinitrile compound is selected from any one or more of malononitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonadinitrile, sebaconitrile, 2-methylsuccinonitrile, tetramethylsuccinonitrile, 2-methylglutaronitrile, 2-methyleneglutaronitrile, ethoxymethylenemalononitrile, 3, 5-dioxa-pimelinonitrile, ethylene glycol bis (propionitrile) ether.
5. The organic electrolyte as claimed in claim 1, wherein the nitrile compound is selected from any one or more compounds having a structure represented by formula 4:
Figure FDA0003927239670000031
in the formula 4, R 8 Is selected from C 1～10 Alkylene or haloalkylene of C 1～10 Alkenylene or haloalkenylene of (A), C 1～10 Alkynyl or haloalkynyl of (A), C 1～10 Or haloalkyleneoxy;
preferably, the trinitrile compound is selected from any one or more of methane trinitrile, 1,3, 6-hexane trinitrile, 1,2, 3-tris (2-cyanato) propane, ethylene-1, 2-trinitrile, 1,2, 3-propane trinitrile, and 1,3, 5-pentane trinitrile.
6. The organic electrolyte as claimed in claim 1, wherein the tetranitrile compound is selected from any one or more compounds having a structure represented by formula 5:
Figure FDA0003927239670000032
in formula 5, R 9 、R 10 Each independently selected from C 1～10 Alkylene or haloalkylene of, C 1～10 Alkenylene or haloalkenylene of (A), C 1～10 Alkynyl or haloalkynyl of C 1～10 Alkylene oxide or haloalkylene oxide of (a);
preferably, the tetranitrile compound is selected from any one or more of tetracyanoethylene, 1,2, 3-propane tetracarbonitrile, methane tetracarbonitrile, 1, 3-propane tetracarbonitrile, and 1, 2-ethane tetracarbonitrile.
7. The organic electrolyte according to claim 1, wherein the bicyclic sulfate compound is contained in an amount of 0.3 to 6% and the nitrile compound is contained in an amount of 1 to 8% based on the total mass of the organic electrolyte.
8. The organic electrolyte as claimed in claim 1, wherein the organic electrolyte further comprises a non-aqueous solvent and a lithium salt;
the non-aqueous solvent is selected from any one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane, sulfolane, tetrahydrofuran, 2-methyl tetrahydrofuran, difluoroethylene carbonate, dimethyl fluorocarbonate, fluoroethyl carbonate, methyl difluoroacetate and ethyl difluoroacetate;
the lithium salt is selected from any one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium difluorophosphate, lithium 4, 5-dicyano-2-trifluoromethylimidazolium, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium tris (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate, lithium difluoro (oxalato) phosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
9. The organic electrolyte as claimed in claim 1, further comprising an additive,
the additive is selected from any one or more of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, 1,3- (1-propylene) sultone, fluoromethyl ethylene carbonate, dimethyl sulfate, vinyl methyl sulfate, propylene sulfate, vinyl sulfite, succinic anhydride, biphenyl, diphenyl ether, toluene, xylene, cyclohexylbenzene, fluorobenzene, p-fluorotoluene, p-fluorobenzyl ether, tert-butyl benzene, tert-amylbenzene, methylene methanedisulfonate, ethylene glycol bis (propionitrile) ether, hexamethyldisilazane, heptamethyldisilazane, dimethyl methylphosphonate, diethyl ethylphosphonate, trimethyl phosphate, triethyl phosphate, triphenyl phosphite, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate and dimethyl sulfoxide.
10. A lithium ion secondary battery comprising the organic electrolyte solution according to any one of claims 1 to 9.
CN202211378131.4A 2022-11-04 2022-11-04 Organic electrolyte and lithium ion secondary battery containing the same Pending CN115528309A (en)

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