CN115332638A - Electrolyte, electrochemical device and electronic device - Google Patents
Electrolyte, electrochemical device and electronic device Download PDFInfo
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- CN115332638A CN115332638A CN202211256597.7A CN202211256597A CN115332638A CN 115332638 A CN115332638 A CN 115332638A CN 202211256597 A CN202211256597 A CN 202211256597A CN 115332638 A CN115332638 A CN 115332638A
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
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- 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 application provides an electrolyte, an electrochemical device and an electronic device, wherein the electrolyte comprises a solvent and an additive, the solvent comprises cyclic carbonate, carboxylic ester and chain carbonate, and based on the mass of the electrolyte, the mass percentage content A% of the cyclic carbonate, the mass percentage content B% of the carboxylic ester and the mass percentage content C% of the chain carbonate meet the following requirements: 1 is more than or equal to (A + C)/B is less than or equal to 3, and A is less than C; the additive comprises a polynitrile compound, and the polynitrile compound comprises at least one of a compound shown in a formula I-A or a compound shown in a formula II-A; based on the mass of the electrolyte, the mass percentage content of the polynitrile compound is D percent, and D is more than or equal to 0.01 and less than or equal to 8. The electrolyte is applied to an electrochemical device, can protect a positive pole piece and improve the gas production phenomenon of the electrolyte, thereby improving the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device.
Description
Technical Field
The present application relates to the field of electrochemistry, and in particular, to an electrolyte, an electrochemical device, and an electronic device.
Background
Because of the advantages of high energy density, long cycle life, no memory effect and the like, the lithium ion battery is widely applied to the fields of smart phones, wearable equipment, consumer-grade unmanned aerial vehicles, electric automobiles and the like. With the wide application of lithium ion batteries in the above fields, the market has increased higher and higher requirements for the energy density of lithium ion batteries, and with the increase of the energy density, the voltage of lithium ion batteries is also increased.
However, the increase of the voltage of the lithium ion battery can aggravate the damage of the positive active material and deteriorate the chemical stability of the electrolyte, and then the normal-temperature cycle performance and the intermittent cycle performance of the lithium ion battery are affected.
Disclosure of Invention
An electrolyte, an electrochemical device, and an electronic device are provided to improve normal-temperature cycle performance and intermittent cycle performance of the electrochemical device.
In the summary of the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery. The specific technical scheme is as follows:
the first aspect of the application provides an electrolyte, which comprises a solvent and an additive, wherein the solvent comprises cyclic carbonate, carboxylic ester and chain carbonate, and based on the mass of the electrolyte, the mass percentage content A% of the cyclic carbonate, the mass percentage content B% of the carboxylic ester and the mass percentage content C% of the chain carbonate satisfy the following requirements: 1 is more than or equal to (A + C)/B is less than or equal to 3, and A is less than C. For example, the value of (a + C)/B may be 1, 1.05, 1.20, 1.32, 1.44, 1.75, 2, 2.14, 2.52, 2.83, 3, or any value between any two of the above numerical ranges.
The additive comprises a polynitrile compound, and the polynitrile compound comprises at least one of a compound shown in a formula I-A or a compound shown in a formula II-A;
In the formula I-A, A 11 、A 12 、A 13 Independently selected from one of formula (I-A1) and formula (I-A2);
In the formula I-A, n is a positive integer of 1 to 8, wherein, when a plurality of A's are present 11 When a plurality of A 11 Which may be the same or different, A 11 、A 12 、A 13 At least two of which are selected from I-A2;
in the formula II-A, Q is independently selected from one of the formula (II-A1) and the formula (II-A2);
In formula II-A, m is selected from 1 or 2, each Q may be the same or different, each R 22 May be the same or different;
R 11 、R 12 、R 13 、R 21 、R 22 、R 23 independently selected from the group consisting of a covalent single bond, substituted or unsubstituted C 1 -C 10 Alkylene of (a), substituted or unsubstituted C 2 -C 10 Alkenylene group of (a), substituted or unsubstituted C 2 -C 10 Alkynylene of (a), substituted or unsubstituted C 6 -C 10 Arylene of (a), substituted or unsubstituted C 3 -C 10 Alicyclic hydrocarbon group of (a), substituted or unsubstituted C 1 -C 10 When substituted, the substituents are selected from halogen; heterocyclylene groups include pyridyl, thienyl or thiazolyl; wherein the content of the first and second substances,
represents a binding site to an adjacent atom;
based on the mass of the electrolyte, the mass percentage content of the polynitrile compound is D percent, and D is more than or equal to 0.01 and less than or equal to 8. For example, D can be 0.01, 0.1, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, or any number between any two of the above numerical ranges.
The high dielectric constant of the cyclic carbonate can promote the dissociation of lithium salt and improve the ion transmission of the electrochemical device in the middle and later stages of charge and discharge cycles, so that the normal-temperature cycle performance of the electrochemical device is improved, but the addition of the cyclic carbonate is not beneficial to the intermittent cycle performance of the battery, and simultaneously, the defect of electrolyte gas generation is brought. The carboxylic ester generally has low viscosity, can improve ion transmission at a lower temperature, but the carboxylic ester has poor stability on the surface of the positive pole piece and is easy to oxidize to generate gas, so that the intermittent cycle performance of the electrochemical device is reduced and the generated gas is increased. The chain carbonate has a wider redox window and can maintain the electrochemical stability of an electrolyte system, but the chain carbonate is easy to be oxidized and reduced to generate gas, so that the intermittent cycle performance of the battery is influenced. On one hand, the polynitrile compound has stronger adsorption effect on the surface of the anode, reduces the contact between the anode and the electrolyte, inhibits the gas generation of the cyclic carbonate at the anode, and can play a role in cooperatively protecting the anode and the cathode by the film forming effect of the cyclic carbonate at the cathode and the protection of the polynitrile on the anode; meanwhile, when a solvent with the mass percent of the cyclic carbonate A, the mass percent of the carboxylate B and the mass percent of the chain carbonate C being more than or equal to 1 (A + C)/B being less than or equal to 3 and A being less than C is adopted, the electrolyte has good ion transmission and infiltration performance and is combined with the solid electrolyte membranes on the surfaces of the positive electrode and the negative electrode, so that the occurrence of interface side reactions of the electrode and the electrolyte is greatly reduced, and the intermittent cycle performance of the battery is improved; in addition, the polynitrile compound and the chain carbonate are added into the electrolyte simultaneously, so that the redox window of the electrolyte is widened, the oxidation resistance of the electrolyte is improved, and the electrochemical device has better intermittent cycle performance. Therefore, the synergistic effect of the polynitrile compound, the cyclic carbonate, the carboxylic ester and the chain carbonate is more beneficial to improving the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device. When the mass percentage content D% of the polynitrile compound is too large, the dynamic performance of the electrochemical device is influenced, so that the electrochemical device generates lithium precipitation, and the circulation of the electrochemical device and the gas generation phenomenon of the electrolyte are influenced.
The inventor finds that the mass percent of the cyclic carbonate A, the mass percent of the carboxylate B and the mass percent of the chain carbonate C in the electrolyte satisfy 1 to (A + C)/B to 3, and A to C, and the type and mass percent D of the polynitrile compound are regulated and controlled within the range of the application, so that the chemical stability of the electrolyte is effectively improved.
In some embodiments of the present application, the mass percentage of the cyclic carbonate a%, the mass percentage of the carboxylate B%, and the mass percentage of the chain carbonate C% satisfy, based on the mass of the electrolyte: a is more than or equal to 17 and less than or equal to 32; b is more than or equal to 15 and less than or equal to 40; c is more than or equal to 25 and less than or equal to 45; a + B + C is more than or equal to 60. For example, a may be 17, 20, 21, 23, 25, 27, 29, 32 or any value between any two of the above numerical ranges. B may be 15, 18, 20, 22, 23, 25, 27, 28, 29, 32, 25, 36, 40, or any value between any two of the above numerical ranges. C may be 25, 27, 30, 34, 35, 36, 40, 45, or any value between any two of the above numerical ranges. The mass percentage content A of the cyclic carbonate, the mass percentage content B of the carboxylic ester and the mass percentage content C of the chain carbonate are regulated and controlled within the ranges, so that the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device are improved.
Preferably, the compound represented by the formula I-A comprises at least one of the compounds represented by the formulae (I-1) to (I-19):
Preferably, the compound represented by the formula II-A comprises at least one of the compounds represented by the formulae (II-1) to (II-21):
In one embodiment of the present application, the polynitrile compound includes 1,3, 6-Hexanetricarbonitrile (HTCN).
In one embodiment of the present application, the additive further comprises a fluorophosphazene compound comprising a compound represented by formula III-A;
In the formula III-A, R 31 Is selected from C 1 -C 4 Alkyl of (C) 6 -C 12 Aryl or C of 6 To C 12 Halogenated aryl of, R 32 And R 33 Independently selected from hydrogen, halogen, C 1 -C 4 Alkyl of (C) 1 -C 4 Alkoxy group of (C) 1 -C 4 Haloalkyl or C 1 -C 4 A haloalkoxy group of (a).
Based on the mass of the electrolyte, the mass percentage content of the fluoro phosphazene compound is E percent, and E is more than or equal to 0.01 and less than or equal to 10. For example, E can be 0.01, 0.1, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between any two of the above numerical ranges.
The fluoro-phosphazene compound is added into the electrolyte, and can capture free radicals of chain reaction in the thermal runaway process, reduce the number of the free radicals and the intensity of the chain reaction, and achieve the purpose of delaying the thermal runaway, so that the safety performance of the electrochemical device is improved; meanwhile, the reduction of free radicals further reduces the tendency of side reactions of the electrolyte at the electrode interface, improves the stability of the solid electrolyte membrane on the surfaces of the anode and the cathode, and improves the high-temperature thickness expansion rate of the electrochemical device. When the mass percentage E% of the fluoro phosphazene compound in the electrolyte is more than 10%, the content is too much, which easily influences the dynamic performance of the electrochemical device and the normal-temperature cycle performance of the electrochemical device. By selecting the fluoro-phosphazene compound and regulating the mass percentage content E% in the range, the safety performance of the electrochemical device is improved on the basis of not influencing the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device.
Preferably, the compound represented by the formula III-A comprises at least one of the compounds represented by the formulae (III-1) to (III-3):
In one embodiment of the present application, the mass percentage of the polynitrile compound and the mass percentage of the fluorophosphazene compound satisfy: D/E is more than or equal to 0.5 and less than or equal to 30, and D + E is less than or equal to 10. Preferably, 0.6. Ltoreq. D/E. Ltoreq.1.5 and 5. Ltoreq. D + E. Ltoreq.8. For example, the value of D/E may be 0.5, 0.6, 1.0, 1.5, 2, 5, 10, 15, 20, 25, 30, or any number between any two of the above numerical ranges. The value of D + E may be 1.0, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between any two of the foregoing ranges of values. The values of D/E and D + E are regulated and controlled within the range, so that the safety performance of the electrochemical device is improved on the basis of not influencing the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device.
In one embodiment of the present application, the cyclic carbonate includes at least one of ethylene carbonate (also referred to as ethylene carbonate, EC for short), propylene carbonate (also referred to as propylene carbonate, PC for short), or ethylene carbonate (VEC). The carboxylic acid ester includes at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl butyrate, methyl isovalerate, propyl hexanoate, or isobutyl acetate. The chain carbonate includes at least one of dimethyl carbonate (DMC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), methyl Propyl Carbonate (MPC), dioctyl carbonate, diamyl carbonate, ethyl isobutyl carbonate, isopropyl methyl carbonate, di-n-butyl carbonate, diisopropyl carbonate, or propyl carbonate. The cyclic carbonate, the carboxylic ester and the chain carbonate are selected, so that the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device can be improved.
In one embodiment of the present application, the electrolyte further includes a lithium salt, which is not particularly limited as long as the object of the present application can be achieved. For example, the lithium salt includes LiPF 6 、LiBF 4 、LiClO 4 、LiB(C 6 H 5 ) 4 、LiCH 3 SO 3 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiC(SO 2 CF 3 ) 3 、LiSiF 6 At least one of LiBOB or LiDFOB; the present application does not specifically limit the mass percentage of the lithium salt in the electrolyte, as long as the object of the present application can be achieved. For example, the lithium salt is present in an amount L% by mass, based on the mass of the electrolyte, of 8. Ltoreq. L.ltoreq.15.
A second aspect of the present application provides an electrochemical device comprising an electrolyte as described in any preceding aspect. Therefore, the electrochemical device has good normal-temperature cycle performance and intermittent cycle performance.
The electrochemical device further comprises a positive pole piece, a negative pole piece, a diaphragm arranged between the positive pole piece and the negative pole piece, a packaging shell and the like. The application has no special limitation on the positive pole piece, the negative pole piece, the diaphragm, the packaging shell and the like in the electrochemical device, and the technical personnel in the field can select the positive pole piece, the negative pole piece, the diaphragm, the packaging shell and the like according to actual needs as long as the purpose of the application can be realized.
The kind of the electrochemical device of the present application is not particularly limited, and it may include any device in which an electrochemical reaction occurs. In some embodiments, the electrochemical device may include, but is not limited to: a lithium metal secondary battery, a lithium ion battery (lithium ion secondary battery), a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like.
The preparation process of the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited, and for example, may include, but is not limited to, the following steps: stacking the positive pole piece, the diaphragm and the negative pole piece in sequence, winding and folding the positive pole piece, the diaphragm and the negative pole piece according to needs to obtain an electrode assembly with a winding structure, putting the electrode assembly into a packaging shell, injecting electrolyte into the packaging shell and sealing the packaging shell to obtain the electrochemical device; or, stacking the positive pole piece, the diaphragm and the negative pole piece in sequence, fixing four corners of the whole lamination structure by using adhesive tapes to obtain an electrode assembly of the lamination structure, placing the electrode assembly into a packaging shell, injecting electrolyte into the packaging shell, and sealing the packaging shell to obtain the electrochemical device. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the package case as necessary to prevent a pressure rise and overcharge/discharge inside the electrochemical device.
A third aspect of the present application provides an electronic device comprising an electrochemical device according to any one of the preceding aspects. Therefore, the electronic device also has good normal-temperature cycle performance and intermittent cycle performance.
The electronic device of the present application is not particularly limited, and may include, but is not limited to, the following categories: notebook computers, pen-input computers, mobile computers, electronic book players, cellular phones, portable facsimile machines, portable copiers, portable printers, head-mounted stereo headphones, video recorders, liquid crystal televisions, portable cleaners, portable CD players, mini-discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting equipment, toys, game machines, clocks, electric tools, flashlights, cameras, large household batteries, and lithium ion capacitors.
The application provides an electrolyte, an electrochemical device and an electronic device, wherein the electrolyte comprises a solvent and an additive, the solvent comprises cyclic carbonate, carboxylic ester and chain carbonate, and based on the mass of the electrolyte, the mass percentage content A% of the cyclic carbonate, the mass percentage content B% of the carboxylic ester and the mass percentage content C% of the chain carbonate satisfy the following conditions: 1 is more than or equal to (A + C)/B is less than or equal to 3, and A is less than C; the additive comprises a polynitrile compound; based on the mass of the electrolyte, the mass percentage content of the polynitrile compound is D percent, and D is more than or equal to 0.01 and less than or equal to 8. The chemical stability of the electrolyte is improved by setting the mass percentage relationship among the cyclic carbonate, the carboxylic ester and the chain carbonate in the electrolyte and setting the type and the content of the additive in the electrolyte, and the electrolyte is applied to an electrochemical device, so that the anode can be protected, the gas production phenomenon of the electrolyte can be improved, and the normal-temperature cycle performance and the intermittent cycle performance of the electrochemical device can be effectively improved.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below with reference to embodiments. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments that can be derived from the embodiments given herein by a person of ordinary skill in the art are intended to be within the scope of the present disclosure.
In the embodiments of the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods.
The test method and the test equipment are as follows:
testing intermittent cycle performance:
the intermittent cycle is a test for simulating the practical use condition of the notebook computer, and consists of a high-temperature cycle part and a storage part, the cycle capacity of the intermittent cycle is comprehensively influenced by the cycle capacity and the storage performance of the lithium ion battery at high temperature, and the specific test flow is as follows:
charging the lithium ion battery to 4.5V at a constant current of 0.5C at 45 ℃, then charging at a constant voltage until the current is 0.05C, measuring the initial full charge thickness of the lithium ion battery, standing for 1170min at 45 ℃, and then discharging to 3.0V at a constant current of 0.5C, wherein the first cycle is adopted. And (4) circulating the lithium ion battery for multiple times according to the conditions, and measuring the full charge thickness of the lithium ion battery in each circulation. And (3) repeatedly carrying out charge and discharge cycles with the capacity of the first discharge as 100 percent until the discharge capacity retention rate is attenuated to 80 percent, stopping testing, recording the number of cycle turns as an index for evaluating the intermittent cycle capacity retention rate of the lithium ion battery, and taking the thickness expansion rate as an index for evaluating the intermittent cycle gas production capacity of the lithium ion battery.
Thickness expansion rate = (thickness at full fill per revolution-initial full fill thickness)/first full fill thickness x 100%.
And taking the cycle number and the thickness expansion rate as the indexes of the intermittent cycle performance of the lithium ion battery.
And (3) testing the normal-temperature cycle performance:
at 25 ℃, the lithium ion battery is charged with a constant current of 1.2 ℃ to 4.25V, charged with a constant voltage of 4.25V to a current of 0.6C, then charged with a constant current of 0.6C to 4.5V, further charged with a constant voltage to 0.05C, and discharged with a constant current of 0.5C to 3.0V, and the first cycle is carried out. And circulating the lithium ion battery for multiple times according to the conditions. And (3) repeatedly carrying out charge and discharge cycles with the capacity of the first discharge as 100 percent until the discharge capacity retention rate is attenuated to 80 percent, stopping testing, and recording the number of cycles as an index for evaluating the normal-temperature cycle performance of the lithium ion battery.
And (3) hot box testing:
charging the lithium ion battery to 4.5V at a constant current of 0.5C at 25 ℃, then charging at a constant voltage until the current is 0.05C, placing the lithium ion battery in a high-temperature box, heating to 135 +/-2 ℃ at a heating speed of 5 +/-2 ℃, keeping for 60min, and recording the changes of the voltage, the temperature and the temperature of the hot box of the lithium ion battery. The lithium ion battery passes the test without fire, explosion and smoke. 5 batteries are tested each time, and the test results are recorded respectively. And taking a hot box test as an index of the safety performance of the lithium ion battery.
Examples 1 to 1
< preparation of electrolyte solution >
In an argon atmosphere glove box having a water content of less than 10ppm, a solvent was obtained by mixing a cyclic carbonate (ethylene carbonate: propylene carbonate mass ratio of 1 6 And (3) uniformly stirring the additive polynitrile compound shown in the formula (I-18) to obtain the electrolyte. Wherein, based on the mass of the electrolyte, liPF 6 The content of the cyclic carbonate is 11.7% by mass, the content of the cyclic carbonate A% by mass is 17% by mass, the content of the carboxylic ester B% by mass is 36% by mass, the content of the chain carbonate C% by mass is 35% by mass, and the content of the polynitrile compound D% by mass is 0.3% by mass.
< preparation of Positive electrode sheet >
LiCoO as positive electrode material 2 And mixing conductive carbon black (Super p) serving as a conductive agent and polyvinylidene fluoride serving as a binder according to a mass ratio of 95. And uniformly coating the positive electrode slurry on one surface of an aluminum foil of a positive electrode current collector with the thickness of 12 mu m, and drying the aluminum foil at 120 ℃ for 1h to obtain the positive electrode plate with the single surface coated with the positive electrode material layer. And repeating the steps on the other surface of the aluminum foil to obtain the positive pole piece with the positive pole material layer coated on the two sides. And then drying for 4 hours at 85 ℃ under vacuum condition, and obtaining the positive pole piece with the specification of 74mm multiplied by 867mm after cold pressing, cutting and cutting.
< preparation of negative electrode sheet >
Mixing the negative electrode material graphite, the binder styrene butadiene rubber and the negative electrode thickener carboxymethylcellulose sodium according to a mass ratio of 95. And uniformly coating the negative electrode slurry on one surface of a copper foil of a negative electrode current collector with the thickness of 12 mu m, and drying the copper foil at 120 ℃ to obtain a negative electrode pole piece with the coating thickness of 130 mu m and the single surface coated with a negative electrode material layer. And repeating the steps on the other surface of the copper foil to obtain the negative pole piece with the negative pole material layers coated on the two surfaces. And then drying for 4 hours at 85 ℃ under a vacuum condition, and obtaining the negative pole piece with the specification of 78mm multiplied by 875mm after cold pressing, cutting and slitting.
< preparation of separator >
A Polyethylene (PE) film having a thickness of 14 μm was used.
< preparation of lithium ion Battery >
And (3) stacking the prepared positive pole piece, diaphragm and negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play a role in isolation, and then winding to obtain the electrode assembly. And (3) putting the electrode assembly into an aluminum plastic film packaging shell, placing the aluminum plastic film packaging shell in a vacuum oven at 85 ℃ for drying for 12 hours to remove water, injecting the prepared electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Examples 1-2 to examples 1-21
The procedure was followed in the same manner as in example 1-1, except that the relevant production parameters were adjusted as in Table 1. The same procedures used in example 1-1 were repeated except that cyclic carbonate, carboxylic ester and chain carbonate were used in the amounts adjusted to the values of A, B and C.
Example 2-1 to example 2-11
The examples were conducted in the same manner as in examples 1 to 14 except that the type and content of the additive fluorophosphazene compound shown in Table 2 were further added in < preparation of electrolyte solution >.
Comparative examples 1-1 to 1-4
The procedure was as in example 1-1, except that the relevant production parameters were adjusted as shown in Table 1.
Comparative example 2-1
The procedure of example 1-1 was repeated, except that the polynitrile compound was not added in < preparation of electrolyte solution > and that the fluoro phosphazene compound as an additive was further added in accordance with the kind and content shown in Table 2.
The production parameters and performance parameters of each example and comparative example are shown in tables 1 to 2.
TABLE 1
Note: the "\\" in Table 1 indicates no relevant preparation parameters.
TABLE 2
Note: the "\\" in Table 2 indicates no relevant preparation parameters.
Referring to table 1, it can be seen from examples 1-1 to 1-21 and comparative examples 1-1 to 1-4 that the number of cycles at normal temperature, the number of cycles at intermittent and the thickness expansion rate at 45 ℃ of the lithium ion battery vary with the values of the relation (a + C)/B of the mass percentage contents of the cyclic carbonate, the carboxylic ester and the chain carbonate in the electrolyte, and the kind and mass percentage content D% of the polynitrile compound. The lithium ion battery with the value of (A + C)/B in the electrolyte, the type and the mass percentage content D% of the polynitrile compound in the range is selected, the number of normal-temperature cycle turns and the number of intermittent cycle turns are more, and the thickness expansion rate at 45 ℃ is lower, so that the normal-temperature cycle performance and the intermittent cycle performance of the lithium ion battery are better.
Among them, as can be seen from examples 1-1 to 1-9 and comparative examples 1-1 to 1-2, the lithium ion battery having the value of (a + C)/B in the electrolyte within the range of the present application has more cycles at normal temperature and intermittent cycles and lower thickness expansion rate at 45 ℃, indicating that the lithium ion battery has better normal temperature cycle performance and intermittent cycle performance.
As can be seen from examples 1-10 to examples 1-16 and comparative examples 1-3, the lithium ion battery with the mass percent D% of the polynitrile compound in the range of the application has more normal-temperature cycle circles and intermittent cycle circles and lower thickness expansion rate at 45 ℃, which shows that the normal-temperature cycle performance and intermittent cycle performance of the lithium ion battery are better.
As can be seen from examples 1 to 4, examples 1 to 11, and examples 1 to 17 to examples 1 to 21, the lithium ion battery having the polynitrile compound within the range of the present application has more cycles at room temperature and intermittent cycles and lower thickness expansion rate at 45 ℃, indicating that the lithium ion battery has better cycle performance at room temperature and intermittent cycle performance.
Referring to table 2, when the polynitrile compound and the fluorophosphazene compound are simultaneously added to the electrolyte as additives, the number of cycles at normal temperature, the capacity retention rate at 45 ℃, the thickness expansion rate at 45 ℃ and the hot box test result of the lithium ion battery are changed along with the type and mass percentage content E% of the fluorophosphazene compound and the change of the values of the mass percentage content relational expressions D/E and D + E of the polynitrile compound and the fluorophosphazene compound. The lithium ion battery with the type and the mass percentage content E% of the fluorophosphazene compound and the mass percentage content relational expression D/E and the value of D + E of the polynitrile compound and the fluorophosphazene compound within the range of the application is selected, the normal-temperature cycle number and the intermittent cycle number are more, the thickness expansion rate at 45 ℃ is lower, and the number of the lithium ion battery passing through a hot box test is more, so that the lithium ion battery has good normal-temperature cycle performance, intermittent cycle performance and safety performance.
Among them, as can be seen from examples 2-1 to 2-3, the lithium ion battery using the fluorophosphazene compound in the range of the present application has more cycles at normal temperature and intermittent cycles, lower thickness expansion rate at 45 ℃, and more passing number in hot box test, indicating that the lithium ion battery has good cycle performance at normal temperature, intermittent cycle performance and safety performance.
As can be seen from examples 1-14, 2-1, 2-4 to 2-11, and 2-1, the multi-nitrile compound and the fluorophosphazene compound are added into the electrolyte at the same time as additives, and the lithium ion battery with the mass percent content E% of the fluorophosphazene compound and the mass percent content relation of the multi-nitrile compound and the fluorophosphazene compound, wherein the values of the formulas D/E and D + E are within the range of the application, has more normal temperature cycle number and intermittent cycle number, lower thickness expansion rate at 45 ℃ and more passing number of hot box tests, and shows that the lithium ion battery has good normal temperature cycle performance, intermittent cycle performance and safety performance.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (12)
1. An electrolyte comprises a solvent and an additive, wherein the solvent comprises cyclic carbonate, carboxylic ester and chain carbonate, and the mass percentage content A% of the cyclic carbonate, the mass percentage content B% of the carboxylic ester and the mass percentage content C% of the chain carbonate satisfy that: 1 is more than or equal to (A + C)/B is less than or equal to 3, and A is less than C;
the additive comprises a polynitrile compound;
based on the mass of the electrolyte, the mass percentage content of the polynitrile compound is D percent, and D is more than or equal to 0.01 and less than or equal to 8.
2. The electrolyte of claim 1, the polynitrile compound comprising at least one of a compound of formula I-a or a compound of formula II-a;
In the formula I-A, A 11 、A 12 、A 13 Independently selected from one of formula (I-A1) and formula (I-A2);
In the formula I-A, n is a positive integer of 1 to 8, wherein, when a plurality of A's are present 11 When a plurality of A 11 Which may be the same or different, said A 11 、A 12 、A 13 At least two of which are selected from I-A2;
in the formula II-A, Q is independently selected from one of the formula (II-A1) and the formula (II-A2);
In formula II-A, m is selected from 1 or 2, each Q may be the same or different, each R 22 May be the same or different;
R 11 、R 12 、R 13 、R 21 、R 22 、R 23 independently selected from the group consisting of a covalent single bond, substituted or unsubstituted C 1 -C 10 Alkylene, substituted or unsubstituted C 2 -C 10 Alkenylene group of (1), substituted or unsubstituted C 2 -C 10 Alkynylene of (2), substituted or unsubstituted C 6 -C 10 Arylene of (a), substituted or unsubstituted C 3 -C 10 Alicyclic hydrocarbon group of (2), substituted or unsubstituted C 1 -C 10 When substituted, the substituents are selected from halogen;
said heterocyclylene group comprises pyridyl, thienyl or thiazolyl;
wherein the content of the first and second substances,
representing the binding site to the adjacent atom.
3. The electrolyte of claim 1, the polynitrile compound comprising 1,3, 6-hexanetricarbonitrile.
4. The electrolyte solution according to claim 1, wherein a mass percentage of the cyclic carbonate a%, a mass percentage of the carboxylic ester B%, and a mass percentage of the chain carbonate C% satisfy at least one of the following conditions based on a mass of the electrolyte solution:
17≤A≤32；
15≤B≤40；
25≤C≤45；
A+B+C≥60。
5. the electrolyte of claim 2, wherein the compound of formula I-a comprises at least one of compounds of formulae (I-1) to (I-19):
6. The electrolyte of claim 2, wherein the compound of formula II-a comprises at least one of compounds of formulae (II-1) to (II-21):
7. The electrolyte of claim 1, wherein the additive further comprises a fluorophosphazene compound comprising a compound represented by formula III-a;
In the formula III-A, R 31 Is selected from C 1 -C 4 Alkyl of (C) 6 -C 12 Aryl or C of 6 To C 12 Halogenated aryl of, R 32 And R 33 Independently selected from hydrogen, halogen, C 1 -C 4 Alkyl of (C) 1 -C 4 Alkoxy group of (1), C 1 -C 4 Haloalkyl or C 1 -C 4 Haloalkoxy of (a);
based on the mass of the electrolyte, the mass percentage content of the fluoro phosphazene compound is E%, and E is more than or equal to 0.01 and less than or equal to 10.
8. The electrolyte of claim 7, wherein the compound of formula III-a comprises at least one of compounds of formulae (III-1) to (III-3):
9. The electrolyte solution according to claim 7, wherein the mass percentage of the polynitrile compound and the mass percentage of the fluorophosphazene compound satisfy: D/E is more than or equal to 0.5 and less than or equal to 30, and D + E is less than or equal to 10.
10. The electrolyte of claim 1, wherein the cyclic carbonate comprises at least one of ethylene carbonate, propylene carbonate, or ethylene carbonate;
the carboxylic acid ester comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl butyrate, methyl isovalerate, propyl hexanoate or isobutyl acetate;
the chain carbonate comprises at least one of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, dioctyl carbonate, dipentyl carbonate, ethyl isobutyl carbonate, isopropyl methyl carbonate, di-n-butyl carbonate, diisopropyl carbonate or propyl carbonate.
11. An electrochemical device comprising the electrolyte of any one of claims 1 to 10.
12. An electronic device comprising the electrochemical device of claim 11.
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