CN111682263B - Application of nitrile compound in preparation of electrolyte for high-voltage battery system - Google Patents

Application of nitrile compound in preparation of electrolyte for high-voltage battery system Download PDF

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CN111682263B
CN111682263B CN202010389691.4A CN202010389691A CN111682263B CN 111682263 B CN111682263 B CN 111682263B CN 202010389691 A CN202010389691 A CN 202010389691A CN 111682263 B CN111682263 B CN 111682263B
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electrolyte
nitrile
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hexanetricarbonitrile
nitrile compound
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CN111682263A (en
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杨勇
杨雪蕊
廖颖
张忠如
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Xiamen University
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • 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

Abstract

The invention discloses an application of nitrile compounds in preparing electrolyte for a high-voltage battery system, wherein the nitrile compounds have a structural formula
Figure DDA0002484485690000011
Wherein n is1、n2And n3Are respectively an integer of 0-10, but not 0 at the same time, RfIs a fluorine-containing functional group. The substitution of the F-containing electron-withdrawing functional group can cooperate with a nitrile functional group to well modify an anode interface layer, so that the high-voltage stability of the battery is further improved; the substitution of the F-containing functional group can effectively improve the reduction potential of nitrile molecules, and a stable LiF-rich interface layer is formed on a graphite or lithium metal negative electrode, so that the incompatibility of nitrile additives to the negative electrode is improved, and the overall high-voltage stability of the soft package full cell is improved.

Description

Application of nitrile compound in preparation of electrolyte for high-voltage battery system
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an application of nitrile compounds in preparation of electrolyte for a high-voltage battery system.
Background
Increasing the energy density, especially the volumetric energy density, of batteries is the focus of current research. There are two methods for increasing the volumetric energy density, one is to develop a positive electrode material with high capacity or high operating voltage; and secondly, optimizing the design structure of the battery, such as improving the compression density and the mass ratio of the anode and the cathode, or reducing the mass fraction of the inactive components. In fact, the compacted density and the optimized mass ratio of the active material, as well as the thickness of the membrane and the current collector, are close to their limits. In particular, reducing the thickness of the separator and current collector increases the energy density of lithium batteries at the expense of safety, which may be one of the causes of recent cellular phone explosions. Therefore, the most feasible method for achieving high energy density of lithium ion batteries is to increase the capacities of the cathode and the anode and to increase the operating voltage of LIBs. However, the decomposition voltage of the currently commercialized carbonate system is 4.3V, and when the decomposition voltage is higher than 4.3V, the electrolyte is decomposed seriously, and a serious gas generation phenomenon is accompanied, so that the service life of the battery is greatly reduced, and a potential safety hazard is caused. In order to further widen the operating voltage of the electrolyte, some nitrile and sulfone additives or solvents having strong oxidation resistance are widely popularized. But the sulfone and nitrile solvents are easy to form a loose interface layer with low ionic conductivity on a negative electrode layer, so that the graphite and lithium metal negative electrodes cannot be well compatible.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the application of nitrile compounds in preparing electrolyte for a high-voltage battery system.
Another object of the present invention is to provide an electrolyte for a high voltage battery system.
The technical scheme of the invention is as follows:
the application of nitrile compound in preparing electrolyte for high-voltage battery system, the structural formula of the nitrile compound is
Figure BDA0002484485670000011
Wherein n is1、n2And n3Are each an integer of 0 to 10, and n1、n2And n3Not simultaneously 0, Rf is a fluorine-containing functional group.
The other technical scheme of the invention is as follows:
an electrolyte for high-voltage battery system contains nitrile compound, organic solvent and non-aqueous electrolyte lithium salt, the nitrile compound has the structural formula
Figure BDA0002484485670000021
Wherein n is1、n2And n3Are each an integer of 0 to 10, and n1、n2And n3Not simultaneously 0, RfIs a fluorine-containing functional group.
In a preferred embodiment of the present invention, the organic solvent includes at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), and 4-fluoroethylene carbonate (FEC).
Further preferably, the organic solvent is at least one of dimethyl carbonate, ethyl methyl carbonate, ethylene carbonate and 4-fluoroethylene carbonate.
In a preferred embodiment of the present invention, the non-aqueous electrolyte lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium bis (sulfonyl fluoride) imide (LiFSI).
Further preferably, the nonaqueous electrolyte lithium salt is lithium hexafluorophosphate
In a preferred embodiment of the invention, the content of the nitrile functional additive compound in the electrolyte is 0.1-5 wt%.
More preferably, the content of the nitrile functional additive compound in the electrolyte is 0.5-3 wt%.
The invention has the beneficial effects that:
1. the substitution of the F-containing electron-withdrawing functional group can cooperate with a nitrile functional group to well modify an anode interface layer, so that the high-voltage stability of the battery is further improved;
2. the substitution of the F-containing functional group can effectively improve the reduction potential of nitrile molecules, and a stable LiF-rich interface layer is formed on a graphite or lithium metal negative electrode, so that the incompatibility of nitrile additives to the negative electrode is improved, and the overall high-voltage stability of the soft package full cell is improved.
Drawings
FIG. 1 is LiCoO according to the present invention in example 1, comparative example 1 and comparative example 22Comparative plot of the cycle capacity retention rate of Li battery. The test temperature is 30 ℃, the charge-discharge multiplying power is 1C, and the charge-discharge voltage range is as follows: 3.0V-4.6V.
Fig. 2 is a graph comparing the cycle capacity retention rates of graphite/Li batteries of example 1, comparative example 1 and comparative example 2 of the present invention. The test temperature is 30 ℃, the charge-discharge multiplying power is 1C, and the charge-discharge voltage range is as follows: 2.5V-0.05V.
FIG. 3 is LiCoO according to the present invention in example 1, comparative example 1 and comparative example 32Comparative plot of the cycle capacity retention rate of Li battery. The test temperature is 30 ℃, the charge-discharge multiplying power is 1C, and the charge-discharge voltage range is as follows: 3.0V-4.6V.
Detailed Description
In a preferred embodiment of the present invention, said RfIs fluorine, trifluoromethanesulfonyl, trifluoromethyl, trifluoroacetyl, pentafluoroethyl or trifluoroethyl.
In a preferred embodiment of the present invention, said n1、n2And n3Are respectively an integer of 2 to 10.
Further preferably, n is1、n2And n3Are respectively an integer of 2 to 6.
In a preferred embodiment of the present invention, (CH) in the formula2)n1、(CH2)n2And (CH)2)n3All contain no branch chain and are all alkyl straight chain.
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
The preparation of the nitrile compounds in the following examples is described with reference to Synthesis and Structure of fluoronitrile (Britton D, Farooq S, Keese R. Helvetica Chimica Act, 1977, 60 (4): 1393-.
Example 1
In a glove box with water content lower than 1ppm and oxygen content lower than 1ppm, preparing the electrolyte of the lithium ion battery: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of the nitrile compound containing a functional group of F substituted 3-trifluoromethyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% FMHTCN) was added to the above electrolyte to prepare a resultant electrolyte, and the test was performed.
The preparation method of the 3-trifluoromethyl-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. Introducing 104g of chlorotrifluoromethane gas into the reaction system, controlling the temperature not to exceed 5 ℃ in the aeration process, and stirring for reaction for 2 hours after the aeration is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product, namely the 3-trifluoromethyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000031
example 2
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to dissolve the system to colorlessClear solution of LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of the nitrile compound 3-fluoro-1, 3, 6-hexanetricarbonitrile (labeled as 1% FHTCN) containing a functional group substitution of F was added to the above electrolyte to prepare a resultant electrolyte, and the test was performed.
The preparation method of the 3-fluoro-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. And (3) introducing 20g of anhydrous hydrogen fluoride gas into the reaction system, controlling the temperature to be not more than 5 ℃ in the aeration process, and stirring for reacting for 2 hours after the aeration is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product of 3-fluoro-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000041
example 3
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of the nitrile compound 3-trifluoromethanesulfonyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% FSHTCN) having a F functional group substitution was added to the above electrolyte to prepare a resultant electrolyte, and the test was performed.
The preparation method of the 3-trifluoromethanesulfonyl-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. Weighing 168g of trifluoromethyl sulfonyl chloride, slowly dropwise adding the trifluoromethyl sulfonyl chloride into a reaction system, controlling the temperature not to exceed 5 ℃ in the dropwise adding process, and stirring and reacting for 2 hours after the dropwise adding is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product, namely the 3-trifluoromethanesulfonyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000051
example 4
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of the nitrile compound 3-trifluoroacetyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% TFEHTCN) containing the F functional group substitution was added to the above electrolyte to prepare a resultant electrolyte for testing.
The preparation method of the 3-trifluoroacetyl-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. And (3) introducing 133g of trifluoroacetyl chloride gas into the reaction system, controlling the temperature to be not more than 5 ℃ in the aeration process, and stirring for reacting for 2 hours after the aeration is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product, namely the 3-trifluoroacetyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000052
example 5
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of 3-pentafluoroethyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% PFHTCN) which is a nitrile compound substituted with F functional groups was added to the above electrolyte, and the resulting electrolyte was formulated and tested (test conditions).
The preparation method of the 3-pentafluoroethyl-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. Introducing 155g of pentafluorochloroethane gas into the reaction system, controlling the temperature to be not more than 5 ℃ in the aeration process, and stirring for reaction for 2 hours after the aeration is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product, namely the 3-pentafluoroethyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000061
example 6
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of 3-trifluoroethyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% TFHTCN), which is a nitrile compound substituted with F functional groups, was added to the above electrolyte to prepare a resultant electrolyte, and the test was performed.
The preparation method of the 3-trifluoroethyl-1, 3, 6-hexanetricarbonitrile comprises the following steps: and (3) putting 161g of hexanetricarbonitrile into the dried three-neck flask, introducing nitrogen into the flask system to ensure the anhydrous and anaerobic conditions of the reaction system, and placing the system into an ice water bath at 0-5 ℃. Adding 300mL of dried tetrahydrofuran as a solvent into the system, stirring and mixing uniformly, weighing an n-hexane solution containing 64g of n-butyllithium, dropwise adding the n-hexane solution into a three-neck flask, controlling the temperature of the system to be not more than 5 ℃ in the period, and stirring and reacting for 0.5h after the addition is finished. 119g of chlorotrifluoroethane gas is introduced into the reaction system, the temperature is controlled not to exceed 5 ℃ in the aeration process, and the reaction is stirred for 2 hours after the aeration is finished. And after the reaction is finished, adding 500mL of ethyl acetate into the system, performing extraction and sterilization by using ice water, separating liquid to obtain an organic phase, washing the organic phase twice by using deionized water, separating liquid to obtain an organic phase, and concentrating to remove a dry solvent to obtain the product, namely the 3-trifluoroethyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000062
comparative example 1
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. The prepared electrolyte is directly tested without adding any nitrile compound.
Comparative example 2
In hands with water content below 1PPM and oxygen content below 1PPMIn the case, preparing the electrolyte of the lithium ion battery: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. The resulting electrolyte was then formulated for testing by adding 1 wt.% of hexane trinitrile (labeled 1% HTCN) that had not undergone F substitution to the above electrolyte.
Comparative example 3
Preparing the electrolyte of the lithium ion battery in a glove box with water content lower than 1PPM and oxygen content lower than 1 PPM: mixing LiPF6Dissolving in mixed solvent of EC and EMC at a mass ratio of 3: 7, stirring and mixing uniformly to finally dissolve the system into colorless transparent solution, wherein LiPF6The concentration of (2) is 1.0 mol/L. Then, 1 wt.% of nitrile compound 2-trifluoromethyl-1, 3, 6-hexanetricarbonitrile (labeled as 1% t-FMHTCN), which has the same substituent as FMHTCN in example 1 but different substitution positions, was added to the electrolyte to prepare a solution for testing.
Wherein the preparation method of the 2-trifluoromethyl-1, 3, 6-hexanetrinitrile comprises the following steps: 141g of tert-butyl 2-cyanoacetate and 67g of 3-butenenitrile are weighed into a three-neck flask, 30g of 60% sodium hydride solid is weighed and added into the flask, 300mL of toluene is weighed and added into the flask as a solvent, the mixture is heated to 85 ℃ and stirred for reaction for 24 hours, after the reaction is finished, a system is filtered to obtain a filtrate, and the filtrate is concentrated and the solvent is evaporated to obtain a liquid. Transferring the liquid obtained by concentration into a three-neck flask, weighing 30g of sodium hydride solid with the content of 60 percent and adding the sodium hydride solid into the flask, weighing 135g of 3-trifluoromethyl-3-acrylonitrile into the flask, weighing 300mL of N, N-dimethylformamide and adding the N, N-dimethylformamide into the flask as a solvent, heating to 110 ℃ for 36 hours for reaction, filtering the system after the reaction is finished to obtain filtrate, concentrating the filtrate to evaporate the solvent to obtain liquid, placing the obtained liquid in an argon atmosphere, heating to 190 ℃, and stirring for 15 minutes to obtain the product 2-trifluoromethyl-1, 3, 6-hexanetricarbonitrile.
The structural formula is as follows:
Figure BDA0002484485670000071
TABLE 1 Cyclic Capacity Retention Rate results
LiCoO2Li, 3-4.6V, 200 times (%) graphite/Li, 2.5-0.05V, 100 times (%)
Example 1 71.5 99.8
Example 2 73.0 99.1
Example 3 69.2 92.3
Example 4 72.3 97.2
Example 5 68.5 93.2
Example 6 67.0 97.4
Comparative example 1 23.9 69.4
Comparative example 2 29.7 77.1
Comparative example 3 37.2 86.2
As shown in FIGS. 1 to 3, the addition of the nitrile compound according to the present invention significantly increases LiCoO as compared with comparative example 12The high-voltage cycle performance of the Li battery at 4.6V can be improved, and the compatibility of the Li battery with graphite can be improved. As seen from comparative example 2, the F-unsubstituted hexanetricarbonitrile was p-LiCoO2Li cell has little effect on high voltage cycle performance at 4.6V, while example 1 has a significantly improved LiCoO performance compared to comparative example 3 in comparison with the nitrile compound 3-trifluoromethyl-1, 3, 6-hexanetricarbonitrile, which is a compound of formula 3-trifluoromethyl-1, 3, 6-hexanetricarbonitrile2The high voltage cycle performance of the Li battery under 4.6V and the compatibility of the Li battery with the graphite cathode show that the positions of fluorine substituents are different, and the influence on the performance of the battery is different.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (6)

1. The application of the nitrile compound in preparing the electrolyte for the high-voltage battery system is characterized in that: the nitrile compound has the structural formula
Figure FDA0003210692020000011
Wherein n is1、n2And n3Are each an integer of 0 to 10, and n1、n2And n3Not simultaneously 0, RfIs trifluoromethanesulfonyl or trifluoroacetyl.
2. The use of claim 1, wherein: n is1、n2And n3Are respectively an integer of 2 to 10.
3. Use according to claim 2, characterized in that: n is1、n2And n3Are respectively an integer of 2 to 6.
4. An electrolyte for a high-voltage battery system, characterized in that: contains nitrile compound, organic solvent and non-aqueous electrolyte lithium salt, the structural formula of said nitrile compound is
Figure FDA0003210692020000012
Wherein n is1、n2And n3Are each an integer of 0 to 10, and n1、n2And n3Not simultaneously 0, RfIs trifluoromethanesulfonyl or trifluoroacetyl.
5. The electrolyte for a high voltage battery system according to claim 4, wherein: n is1、n2And n3Are respectively an integer of 2 to 10.
6. The electrolyte for a high voltage battery system according to claim 4, wherein: n is1、n2And n3Are respectively an integer of 2 to 6.
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