CN112072180A - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN112072180A CN112072180A CN202011034766.3A CN202011034766A CN112072180A CN 112072180 A CN112072180 A CN 112072180A CN 202011034766 A CN202011034766 A CN 202011034766A CN 112072180 A CN112072180 A CN 112072180A
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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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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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 invention belongs to the field of lithium ion battery materials, and particularly relates to an electrolyte and a lithium ion battery comprising the same. The silicon-oxygen cyclic compound shown in the formula (I) in the electrolyte provided by the invention and the lithium difluorophosphate cooperate to generate a composite passive film containing a Si-O-Si cross-linking structure and a fluorine-containing inorganic lithium salt on the surface of a negative electrode in the charge-discharge process of the battery, the passive film is firm, tough and low in impedance, the reduction decomposition of a non-aqueous organic solvent is inhibited, the chemical dynamic performance of a negative electrode interface is obviously improved, lithium ions are efficiently transferred, the internal resistance of the battery is effectively reduced, and the low-temperature discharge performance is improved; meanwhile, the silicon-oxygen cyclic compound shown in the formula (I) can be subjected to ring opening and complexing with the anode to form a similar protective layer, the anode interface is improved, the side reaction decomposition of metal ions dissolved out and catalyzed by the electrolyte is inhibited, and the high-temperature storage and safety performance of the battery are effectively improved.
Description
Technical Field
The invention belongs to the field of electrolyte for lithium ion batteries, and particularly relates to electrolyte and a lithium ion battery comprising the same.
Background
In recent years, lithium ion batteries have been widely used in the fields of digital, energy storage, power, military aerospace, communication equipment, and the like. However, with diversification of electronic devices and diversification of functions, consumers have increasingly raised use environments and demands for lithium ion batteries, which requires that lithium ion batteries have properties of high and low temperature performance. Meanwhile, the lithium ion battery has potential safety hazards in the use process, and serious safety accidents, fire and even explosion easily occur under some extreme use conditions such as excessive charging and discharging when the battery is continuously used.
The electrolyte is used as an important component of the lithium ion battery and has great influence on the performance of the battery. Therefore, there is a need to develop a high-safety electrolyte for lithium ion batteries, and a lithium ion battery composed of the electrolyte is required to have good high-temperature storage and low-temperature charge and discharge properties. However, it is often difficult to simultaneously achieve high and low temperature performance with current electrolyte additives. Therefore, it is urgently required to develop an electrolyte capable of widening the use temperature of a lithium ion battery and improving the safety performance of the battery.
Disclosure of Invention
The invention provides an electrolyte for a lithium ion battery and the lithium ion battery comprising the same, aiming at solving the problems that the existing electrolyte is difficult to simultaneously give consideration to and improve the high-low temperature performance, the safety performance and the like of the lithium ion battery.
Specifically, the invention provides the following technical scheme:
an electrolyte for a lithium ion battery, the electrolyte comprising a non-aqueous organic solvent, an additive, and a conductive lithium salt; wherein the additive comprises lithium difluorophosphate and a siloxane cyclic compound shown as a formula (I);
in the formula (I), n is an integer of more than or equal to 0;
r is the same or different and is respectively and independently selected from cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, carbon-containing cyclic ester group, sulfur-containing cyclic ester group, boron-containing cyclic ester group or phosphorus-containing cyclic ester group; the substituent is halogen and alkyl.
Further, R is the same or different and is independently selected from cyano, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C6-12An aryl group, a carbon-containing cyclic ester group, a sulfur-containing cyclic ester group, a boron-containing cyclic ester group or a phosphorus-containing cyclic ester group; the substituent is halogen or C1-6An alkyl group.
Further, R is the same or different and is independently selected from cyano, substituted or unsubstituted C1-3Alkyl, substituted or unsubstituted C2-3Alkenyl, substituted or unsubstituted C2-3Alkynyl, substituted or unsubstituted phenyl, carbon-containing cyclic ester group, sulfur-containing cyclic ester group, boron-containing cyclic ester group or phosphorus-containing cyclic ester group; the substituent is F, Cl or C1-3An alkyl group.
Further, R is the same or different and is independently selected from cyano, 1,2, 3-trifluoropropyl, phenyl, a carbon-containing cyclic ester group, a sulfur-containing cyclic ester group, a boron-containing cyclic ester group or a phosphorus-containing cyclic ester group.
Further, n is an integer between 0 and 4, for example n is 0, 1,2,3 or 4.
Further, the structure of the sulfur-containing cyclic ester group is
Further, the structure containing the carbon cyclic ester group is
Further, the siloxane cyclic compound is selected from at least one of the compounds shown in the following formulas T1-T12:
further, the silicon oxygen cyclic compound represented by the formula (I) is used in an amount of 0.1 to 5 wt%, preferably 0.2 to 2.0 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 5.0 wt% based on the total mass of the electrolyte.
Further, the lithium difluorophosphate is used in an amount of 0.1 to 2 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt% based on the total mass of the electrolyte.
Further, the mass ratio of the siloxy cyclic compound shown in the formula (I) to lithium difluorophosphate is 1-20:1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 and 20: 1.
Further, the additive also comprises at least one of succinonitrile, adiponitrile, 1,3, 6-hexanetrinitrile, 1, 2-bis (cyanoethoxy) ethane, fluoroethylene carbonate and 1, 3-propane sultone, and the additive is used in an amount of 0 to 10 wt%, for example, 0 to 8 wt% based on the total mass of the electrolyte.
Further, the non-aqueous organic solvent is selected from at least one of carbonate, carboxylic ester and fluoroether, wherein the carbonate is selected from one or more of ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and methyl propyl carbonate; the carboxylic ester is selected from one or more of ethyl propionate and propyl propionate; the fluoroether is selected from 1,1,2, 3-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
Further, the conductive lithium salt is selected from any one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide and lithium hexafluorophosphate and a mixture of the above.
Further, the amount of the conductive lithium salt is 10 to 18 wt%, for example, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt% based on the total mass of the electrolyte.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
mixing a non-aqueous organic solvent, an additive and a conductive lithium salt, wherein the additive comprises lithium difluorophosphate and a siloxane cyclic compound shown as a formula (I).
Illustratively, the method comprises the steps of:
preparing a non-aqueous organic solvent in a glove box filled with argon and qualified in water oxygen content, and then quickly adding fully dried conductive lithium salt, lithium difluorophosphate and a siloxane cyclic compound shown in a formula (I) into the non-aqueous organic solvent to prepare the electrolyte.
The invention also provides a lithium ion battery which comprises the electrolyte.
Further, the lithium ion battery also comprises a positive plate, a negative plate and a diaphragm.
Further, the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on one side or two sides of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material selected from artificial graphite or natural graphite.
Further, the anode active material layer further includes a binder, a conductive agent, and a dispersant.
Further, the mass percentage of each component in the negative electrode active material layer is as follows: 70-99.7 wt% of negative electrode active material, 0.1-10 wt% of binder, 0.1-10 wt% of dispersant and 0.1-10 wt% of conductive agent.
Preferably, the negative electrode active material layer comprises the following components in percentage by mass: 76-98.5 wt% of negative electrode active material, 0.5-8 wt% of binder, 0.5-8 wt% of dispersant and 0.5-8 wt% of conductive agent.
Still preferably, the negative electrode active material layer contains the following components in percentage by mass: 85-98.5 wt% of negative electrode active material, 0.5-5 wt% of binder, 0.5-5 wt% of dispersant and 0.5-5 wt% of conductive agent.
Further, the binder is at least one selected from among high polymer polymers such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyethyleneimine (PEI), Polyaniline (PAN), polyacrylic acid (PAA), sodium alginate, Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC), phenol resin, epoxy resin, and the like.
Further, the dispersant is selected from at least one of Polypropylene (PVA), cetylammonium bromide, sodium dodecylbenzenesulfonate, a silane coupling agent, ethanol, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), etc., and more preferably at least one of cetylammonium bromide, sodium dodecylbenzenesulfonate, a silane coupling agent, and ethanol.
Further, the conductive agent is selected from at least one of Carbon Nanotubes (CNTs), carbon fibers (VGCF), conductive graphite (KS-6, SFG-6), mesocarbon microbeads (MCMB), graphene, Ketjen black, Super P, acetylene black, conductive carbon black or hard carbon.
Further, the positive plate comprises a positive current collector and a positive active material layer coated on one side or two sides of the positive current collector, wherein the positive active material layer comprises a positive active material selected from lithium cobaltate (LiCoO)2) Ternary material (LiNiCoAlO)2Or LiNiCoMnO2) Lithium manganate (LiMn)2O4) Lithium iron phosphate (LiFePO)4)、LixNiyM1-yO2Wherein x is more than or equal to 0.9 and less than or equal to 1.2, and y is more than or equal to 0.5<1, M is selected from one or more of Co, Mn, Al, Mg, Ti, Zr, Fe, Cr, Mo, Cu and Ca.
Further, the positive electrode active material layer further includes a binder and a conductive agent.
Further, the mass percentage of each component in the positive active material layer is as follows: 80-99.8 wt% of positive active material, 0.1-10 wt% of binder and 0.1-10 wt% of conductive agent.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 84-99 wt% of positive electrode active material, 0.5-8 wt% of binder and 0.5-8 wt% of conductive agent.
Still preferably, the mass percentage of each component in the positive electrode active material layer is: 90-99 wt% of positive electrode active substance, 0.5-5 wt% of binder and 0.5-5 wt% of conductive agent.
Further, the binder is at least one selected from among high polymer polymers such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyethyleneimine (PEI), Polyaniline (PAN), polyacrylic acid (PAA), sodium alginate, Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC), phenol resin, epoxy resin, and the like.
Further, the conductive agent is selected from at least one of Carbon Nanotubes (CNTs), carbon fibers (VGCF), conductive graphite (KS-6, SFG-6), mesocarbon microbeads (MCMB), graphene, Ketjen black, Super P, acetylene black, conductive carbon black or hard carbon.
Further, the separator is a separator known in the art, such as a polyethylene separator, a polypropylene separator, and the like.
The invention also provides a preparation method of the lithium ion battery, which comprises the following steps:
(1) preparing a positive plate and a negative plate, wherein the positive plate contains a positive active substance, and the negative plate contains a negative active substance;
(2) mixing a nonaqueous organic solvent, an additive and a conductive lithium salt to prepare an electrolyte;
(3) winding the positive plate, the diaphragm and the negative plate to obtain a naked battery cell without liquid injection; and (3) placing the bare cell in an outer packaging foil, injecting the electrolyte in the step (2) into the dried bare cell, and preparing to obtain the lithium ion battery.
Has the advantages that:
the silicon-oxygen cyclic compound shown in the formula (I) and the lithium difluorophosphate in the electrolyte provided by the invention cooperate with each other to generate a composite passive film containing a Si-O-Si cross-linking structure and a fluorine-containing inorganic lithium salt on the surface of a negative electrode in the charging and discharging processes of the battery, the passive film is firm, tough and low in impedance, can inhibit the reductive decomposition of a non-aqueous organic solvent, obviously improves the chemical and dynamic performance of a negative electrode interface, allows lithium ions to efficiently migrate, effectively reduces the internal resistance of the battery, and improves the low-temperature discharging performance; meanwhile, the silicon-oxygen cyclic compound shown in the formula (I) can be subjected to ring opening and complexing with the anode to form a similar protective layer, so that an anode interface is improved, the side reaction decomposition of metal ions dissolved out to catalyze the electrolyte is inhibited, and the high-temperature storage and safety performance of the battery are effectively improved; according to the invention, the silicon-oxygen cyclic compound shown in the formula (I) and the lithium difluorophosphate are added into the electrolyte, so that the safety of the lithium ion battery can be improved, and the excellent high-temperature storage and low-temperature discharge performance can be simultaneously considered.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative examples 1 to 3 and examples 1 to 13
The lithium ion batteries of comparative examples 1 to 3 and examples 1 to 13 were each prepared according to the following preparation method, except for the selection and addition of additives, and the specific differences are shown in table 1.
(1) Preparation of positive plate
LiCoO as positive electrode active material2Mixing polyvinylidene fluoride (PVDF) serving as a binder and acetylene black serving as a conductive agent according to a weight ratio of 96.5:2:1.5, adding N-methylpyrrolidone (NMP), and stirring under the action of a vacuum stirrer until a mixed system becomes uniform and flowable anode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 9-12 mu m; baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, drying the aluminum foil in a baking oven at 120 ℃ for 8 hours, and rolling and cutting to obtain the required positive plate.
(2) Preparation of graphite negative plate
Preparing a graphite negative electrode material with the mass ratio of 95.9 wt%, a single-walled carbon nanotube (SWCNT) conductive agent with the mass ratio of 0.1 wt%, a conductive carbon black (SP) conductive agent with the mass ratio of 1 wt%, a sodium carboxymethylcellulose (CMC) dispersing agent with the mass ratio of 1 wt% and a Styrene Butadiene Rubber (SBR) binder with the mass ratio of 2 wt% into negative electrode slurry by a wet process; uniformly coating the negative electrode slurry on a copper foil with the thickness of 9-12 mu m; and baking the coated copper foil in 5 sections of baking ovens with different temperature gradients, drying the copper foil in an oven at 85 ℃ for 5 hours, and rolling and slitting to obtain the required graphite negative electrode sheet.
(3) Preparation of electrolyte
Uniformly mixing ethylene carbonate, propylene carbonate, diethyl carbonate and propyl propionate according to the mass ratio of 2:2:2:4 in a glove box filled with argon and qualified in water oxygen content (the solvent needs to be normalized), and then quickly adding 12.5 wt% of fully dried lithium hexafluorophosphate (LiPF)6) 5 wt% of fluoroethylene carbonate, 1 wt% of succinonitrile and 1 wt% of adiponitrile, and lithium difluorophosphate and a siloxy cyclic compound represented by the formula (I) (the specific amounts and choices of lithium difluorophosphate and the siloxy cyclic compound represented by the formula (I) are shown in Table 1), and the electrolyte is obtained by uniformly mixing.
(4) Preparation of the separator
The polyethylene diaphragm with the thickness of 7-9 μm is selected.
(5) Preparation of lithium ion battery
Winding the prepared positive plate, the diaphragm and the prepared negative plate to obtain a naked battery cell without liquid injection; placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain the required lithium ion battery.
TABLE 1 compositions of lithium ion batteries prepared in comparative examples 1-3 and examples 1-13
| Item | Siloxane cyclics/wt% | Lithium difluorophosphate/wt.% | Mass ratio of |
| Comparative example 1 | / | / | - |
| Comparative example 2 | 1 wt% of T1 | / | - |
| Comparative example 3 | / | 0.5wt％ | - |
| Example 1 | 1 wt% of T1 | 0.5wt％ | 2:1 |
| Example 2 | 0.8 wt.% of T2 | 0.2wt％ | 4:1 |
| Example 3 | 0.1 wt.% of T3 | 0.1wt％ | 1:1 |
| Example 4 | 2 wt% of T4 | 0.8wt％ | 2.5:1 |
| Example 5 | 3 wt% of T5 | 0.4wt％ | 7.5:1 |
| Example 6 | 2.5 wt.% of T6 | 2.0wt％ | 1.25:1 |
| Example 7 | 4 wt% of T7 | 1.2wt％ | 3.33:1 |
| Example 8 | 5 wt% of T8 | 1.5wt％ | 3.33:1 |
| Example 9 | 1.6 wt.% of T9 | 1.0wt％ | 1.6:1 |
| Example 10 | 3.5 wt.% of T10 | 1.6wt％ | 2.2:1 |
| Example 11 | 0.5 wt.% of T11 | 0.3wt％ | 1.67:1 |
| Example 12 | 2.2 wt.% of T12 | 1.8wt％ | 1.2:1 |
| Example 13 | 0.25 wt.% of T1 | 0.5wt％ | 1:2 |
The lithium ion batteries in the above examples and comparative examples were tested for electrochemical performance under the following specific test conditions:
(1) high temperature storage experiment at 60 ℃: the batteries obtained in the above examples and comparative examples were subjected to a charge-discharge cycle test at room temperature for 3 times at a charge-discharge rate of 0.5C, and then a 0.5C constant current charge cutoff current was 0.025C, and the full charge state was reached, and the maximum discharge capacity Q of the previous 3 cycles of 0.5C was recorded1And battery thickness T1. The fully charged battery was stored at 60 ℃ for 30 days, and the battery thickness T after 30 days was recorded2And 0.5C discharge capacity Q2Experimental data such as the thickness change rate and the capacity retention rate of the battery stored at high temperature were calculated from the following formulas, and the results are reported in table 2.
Thickness change rate (%) - (T)2-T1)/T1×100％；
Capacity retention (%) ═ Q2/Q1×100％。
(2)1Low temperature discharge experiment at 0 ℃: the batteries obtained in the above examples and comparative examples were subjected to 10 charge-discharge cycles at 0.7C rate at room temperature, and then charged to a full charge state at 0.7C rate, and the charge capacity Q was recorded3. Laying the battery at-10 deg.C for 4h, discharging to 3V at 0.4C rate, and recording discharge capacity Q4The low-temperature discharge capacity retention was calculated from the following formula, and the recorded results are shown in table 2.
Capacity retention (%) ═ Q4/Q3×100。
(3) Overcharge experiment:
the cells obtained in the above examples and comparative examples were constant-current charged at 3C rate to 5V at room temperature to record the state of the cell, and the results are reported in table 2.
TABLE 2 results of experimental tests of comparative examples 1-3 and examples 1-13
As can be seen from comparative examples 1 to 3 and example 1, the siloxane cyclic compound and lithium difluorophosphate significantly improved the low-temperature discharge performance of the battery; meanwhile, the silicon-oxygen cyclic compound effectively improves the high-temperature storage and safety performance of the battery; further, as can be seen from comparison of examples 1 to 12 with example 13, the cell performance is better when the addition ratio of the siloxy cyclic compound to lithium difluorophosphate is in the range of 1 to 20: 1.
In summary, according to the electrolyte and the lithium ion battery provided by the invention, the safety of the lithium ion battery can be improved, and the excellent high-temperature storage and low-temperature discharge performance can be considered at the same time.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrolyte, wherein the electrolyte comprises a non-aqueous organic solvent, an additive, and a conductive lithium salt; wherein the additive comprises lithium difluorophosphate and a siloxane cyclic compound shown as a formula (I);
in the formula (I), n is an integer of more than or equal to 0;
r is the same or different and is respectively and independently selected from cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, carbon-containing cyclic ester group, sulfur-containing cyclic ester group, boron-containing cyclic ester group or phosphorus-containing cyclic ester group; the substituent is halogen and alkyl.
2. The electrolyte of claim 1, wherein R, which are the same or different, are each independently selected from cyano, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C6-12An aryl group, a carbon-containing cyclic ester group, a sulfur-containing cyclic ester group, a boron-containing cyclic ester group or a phosphorus-containing cyclic ester group; the substituent is halogen or C1-6An alkyl group; and/or the presence of a gas in the gas,
r is the same or different and is independently selected from cyano, substituted or unsubstituted C1-3Alkyl, substituted or unsubstituted C2-3Alkenyl, substituted or unsubstituted C2-3Alkynyl, substituted or unsubstituted phenyl, carbon-containing cyclic ester group, sulfur-containing cyclic ester group, boron-containing cyclic ester group or phosphorus-containing cyclic ester group; the substituent is F, Cl or C1-3An alkyl group; and/or the presence of a gas in the gas,
r is the same or different and is independently selected from cyano, 1,2, 3-trifluoropropyl, phenyl, carbon-containing cyclic ester group, sulfur-containing cyclic ester group, boron-containing cyclic ester group or phosphorus-containing cyclic ester group.
3. The electrolyte of claim 1 or 2, wherein n is an integer between 0 and 4, such as n is 0, 1,2,3 or 4.
4. The electrolyte of any one of claims 1 to 3, wherein the siloxane cyclic compound is selected from at least one of the compounds represented by the following formulas T1-T12:
5. the electrolyte according to any one of claims 1 to 4, wherein the siloxane cyclic compound of formula (I) is used in an amount of 0.1 to 5 wt% based on the total mass of the electrolyte; and/or the presence of a gas in the gas,
the dosage of the lithium difluorophosphate accounts for 0.1 to 2 weight percent of the total mass of the electrolyte.
6. The electrolyte according to any one of claims 1 to 5, wherein the mass ratio of the siloxane cyclic compound represented by formula (I) to lithium difluorophosphate is 1-20: 1.
7. The electrolyte of any of claims 1-6, wherein the additive further comprises at least one of succinonitrile, adiponitrile, 1,3, 6-hexanetricarbonitrile, 1, 2-bis (cyanoethoxy) ethane, fluoroethylene carbonate, and 1, 3-propane sultone in an amount of 0-10 wt.% based on the total mass of the electrolyte.
8. The electrolyte of any one of claims 1-7, wherein the non-aqueous organic solvent is selected from at least one of a carbonate, a carboxylate, and a fluoroether, wherein the carbonate is selected from one or more of ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, and methylpropyl carbonate; the carboxylic ester is selected from one or more of ethyl propionate and propyl propionate; the fluoroether is selected from 1,1,2, 3-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
9. The electrolyte of any one of claims 1-8, wherein the conductive lithium salt is selected from any one of or a mixture of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, and lithium hexafluorophosphate; and/or the presence of a gas in the gas,
the dosage of the conductive lithium salt accounts for 10-18 wt% of the total mass of the electrolyte.
10. A lithium ion battery comprising the electrolyte of any of claims 1-9.
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| CN112768770A (en) * | 2021-01-19 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN113889666A (en) * | 2021-10-20 | 2022-01-04 | 天津力神电池股份有限公司 | Lithium ion battery electrolyte additive, lithium ion battery electrolyte and application |
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| CN114335723A (en) * | 2021-12-27 | 2022-04-12 | 珠海市赛纬电子材料股份有限公司 | Additive, non-aqueous electrolyte containing additive and lithium ion battery |
| CN114464884A (en) * | 2022-01-21 | 2022-05-10 | 珠海冠宇电池股份有限公司 | Electrolyte and battery containing silicon-based negative electrode and comprising electrolyte |
| EP4160775A1 (en) * | 2021-09-29 | 2023-04-05 | Zhuhai Smoothway Electronic Materials Co., Ltd. | Additive, electrolyte, and lithium-ion battery using the same |
| CN116231091A (en) * | 2023-05-08 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Electrolyte for lithium secondary battery, and electricity using device |
| CN117154214A (en) * | 2023-10-30 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Electrolyte, secondary battery and electricity utilization device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894974A (en) * | 2005-10-20 | 2010-11-24 | 三菱化学株式会社 | Lithium secondary battery and use therein nonaqueous electrolytic solution |
| CN104380517A (en) * | 2012-06-13 | 2015-02-25 | 中央硝子株式会社 | Electrolyte for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using same |
| US20190288339A1 (en) * | 2016-07-22 | 2019-09-19 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, secondary battery, and module |
-
2020
- 2020-09-27 CN CN202011034766.3A patent/CN112072180A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894974A (en) * | 2005-10-20 | 2010-11-24 | 三菱化学株式会社 | Lithium secondary battery and use therein nonaqueous electrolytic solution |
| CN104380517A (en) * | 2012-06-13 | 2015-02-25 | 中央硝子株式会社 | Electrolyte for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using same |
| US20150171475A1 (en) * | 2012-06-13 | 2015-06-18 | Central Glass Company, Limited | Electrolyte for Non-Aqueous Electrolyte Battery, and Non-Aqueous Electrolyte Battery Using Same |
| CN104380517B (en) * | 2012-06-13 | 2018-01-02 | 中央硝子株式会社 | Battery with nonaqueous electrolyte electrolyte and use its battery with nonaqueous electrolyte |
| US20190288339A1 (en) * | 2016-07-22 | 2019-09-19 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, secondary battery, and module |
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| CN112768770A (en) * | 2021-01-19 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| EP4160775A1 (en) * | 2021-09-29 | 2023-04-05 | Zhuhai Smoothway Electronic Materials Co., Ltd. | Additive, electrolyte, and lithium-ion battery using the same |
| CN113889666A (en) * | 2021-10-20 | 2022-01-04 | 天津力神电池股份有限公司 | Lithium ion battery electrolyte additive, lithium ion battery electrolyte and application |
| CN114094167A (en) * | 2021-11-23 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Battery with improved battery capacity |
| CN114094167B (en) * | 2021-11-23 | 2023-12-19 | 珠海冠宇电池股份有限公司 | Battery cell |
| CN114335723A (en) * | 2021-12-27 | 2022-04-12 | 珠海市赛纬电子材料股份有限公司 | Additive, non-aqueous electrolyte containing additive and lithium ion battery |
| CN114335723B (en) * | 2021-12-27 | 2022-09-06 | 珠海市赛纬电子材料股份有限公司 | Additive, and non-aqueous electrolyte and lithium ion battery containing additive |
| CN114464884A (en) * | 2022-01-21 | 2022-05-10 | 珠海冠宇电池股份有限公司 | Electrolyte and battery containing silicon-based negative electrode and comprising electrolyte |
| CN116231091A (en) * | 2023-05-08 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Electrolyte for lithium secondary battery, and electricity using device |
| CN116231091B (en) * | 2023-05-08 | 2023-08-29 | 宁德时代新能源科技股份有限公司 | Electrolyte for lithium secondary battery, and electricity using device |
| CN117154214A (en) * | 2023-10-30 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Electrolyte, secondary battery and electricity utilization device |
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