CN114464883B - High-voltage electrolyte and battery containing same - Google Patents
High-voltage electrolyte and battery containing same Download PDFInfo
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- CN114464883B CN114464883B CN202210039436.6A CN202210039436A CN114464883B CN 114464883 B CN114464883 B CN 114464883B CN 202210039436 A CN202210039436 A CN 202210039436A CN 114464883 B CN114464883 B CN 114464883B
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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
- H01M10/056—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
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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
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Abstract
The invention provides a high-voltage electrolyte and a battery containing the same, wherein the electrolyte comprises electrolyte salt, an organic solvent and an additive, and the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from 1,1' -sulfuryl diimidazole compounds. According to the invention, through the synergistic effect of the first additive and the second additive, the film can be formed on the surface of the positive electrode, the direct contact of the electrode material and the electrolyte is avoided, the microstructure of the electrode material is stabilized, the dissolution of transition metal elements at high temperature is reduced, the SEI film can be formed on the surface of the negative electrode material, the reduction reaction of the solvent at the interface of the negative electrode is inhibited, and the high-temperature storage performance, the high-temperature circulation performance, the low-temperature discharge performance and the thermal shock performance of the battery under high voltage can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a high-voltage electrolyte and a battery containing the same.
Background
The battery is widely used by people due to the characteristics of high working voltage, large specific energy, long cycle life, no memory effect and the like, and the battery is generally applied to the field of 3C digital consumer electronic products at present. With the advent of the 5G age, higher demands have been made on the energy density of batteries, and increasing the charge cutoff voltage of batteries is one of the important means to increase energy density.
The electrolyte serves as a blood vessel of the battery and plays a critical role in improving the charge cut-off voltage of the battery. This is mainly because the electrolyte continues to undergo oxidative decomposition reaction at the surface of the positive electrode under high voltage, resulting in serious deterioration of high-temperature (45 ℃ or more) storage performance and thermal shock performance of the battery, failing to meet customer and project performance requirements.
In view of the above, it is necessary to develop a high-voltage electrolyte that can effectively improve the high-temperature storage performance and thermal shock performance of the battery while achieving both dynamic performance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-voltage electrolyte and a battery containing the same, and the electrolyte can ensure the dynamic performance of the battery under high pressure, and effectively improve the high-temperature cycle performance, the low-temperature discharge performance, the high-temperature storage performance and the thermal shock performance of the battery.
The invention aims at realizing the following technical scheme:
an electrolyte comprising an electrolyte salt, an organic solvent, and an additive, the additive comprising a first additive and a second additive;
the first additive is selected from sulfonamide compounds, and the second additive is selected from 1,1' -sulfuryl diimidazole compounds.
According to an embodiment of the present invention, the first additive may be obtained after commercial purchase or may be prepared using methods known in the art.
According to an embodiment of the present invention, the first additive is selected from at least one of a compound represented by formula I or a compound represented by formula II:
in the formula I and the formula II, R 1 Selected from substituted or unsubstituted aryl groups, if substituted aryl groups, said substituents being selected from alkyl, haloalkyl or halogen;
in the formula I, R 2 And R is 3 The same or different, independently of one another, from alkyl groups;
in formula II, the N-containing ring group is a saturated ring group containing at least one N atom.
According to an embodiment of the invention, in formula I and formula II, R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and the substituents are selected from the group consisting of C 1-6 Alkyl (e.g. C 1-4 Alkyl, in particular methyl, ethyl, n-propyl, iso-propylPropyl, n-butyl, isobutyl or tert-butyl), halogenated C 1-6 Alkyl (e.g. halogenated C 1-4 Alkyl, in particular halomethyl, haloethyl, halon-propyl, haloisopropyl, halon-butyl, haloisobutyl or halotert-butyl, in particular trifluoromethyl) or halogen (for example F, cl, br or I, in particular F).
According to an embodiment of the invention, in formula I, R 2 And R is 3 Identical or different, independently of one another, from C 1-6 Alkyl radicals, e.g. C 1-4 Alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
According to an embodiment of the invention, in formula II, the N-ring containing group is unsubstituted or optionally substituted with one or more R's containing at least one N atom a Substituted saturated cyclic groups;
R a is halogen, -CN, -NO 2 、-NH 2 、-CO-NH 2 Unsubstituted or optionally substituted by one or more R b Substituted as follows: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl;
R b is halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl groups.
According to an embodiment of the invention, in formula II, the saturated cyclic group is a 4-10 membered saturated cyclic group (e.g. a 5-8 membered saturated cyclic group, in particular a 5-membered saturated cyclic group, a 6-membered saturated cyclic group, a 7-membered saturated cyclic group or an 8-membered saturated cyclic group).
According to an embodiment of the present invention, in formula II, the number of heteroatoms in the N-ring containing group may be one, two or more than three. When two or more heteroatoms are present, one is an N atom, and the other may be at least one of an N atom, an O atom, or an S atom.
According to an embodiment of the present invention, in formula II, the N-ring containing group is selected from one of the N-ring containing groups shown below:
wherein, represent the connection.
According to an embodiment of the present invention, the first additive is selected from at least one of the following compounds 1 to 8:
according to an embodiment of the present invention, the second additive may be obtained commercially or may be prepared by methods known in the art.
According to an embodiment of the present invention, the second additive is selected from at least one of the compounds represented by formula III:
in formula III, n 1 0, 1, 2 or 3; n is n 2 0, 1, 2 or 3;
R 4 and R is 5 Identical or different, independently of one another, from H, halogen, cyano, unsubstituted or optionally substituted by one, two or more R' a Substituted with the following groups: c (C) 1-6 Alkyl, C 2-6 Alkenyl, C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, sulfo (-SO) 3 H)；
Each R' a The same or different, independently of one another, are selected from halogen, C 1-6 An alkyl group.
According to an embodiment of the invention, in formula III, R 4 And R is 5 The same or different, independently of one another, from H, propenyl, halogen, C 1-3 Alkyl, methoxy, trifluoromethyl, C 1-3 Alkoxycarbonyl, cyano or-SO 3 F。
According to an embodiment of the invention, the second additive is selected from at least one of compounds 9 to 14:
as the electrolyte according to the present invention, the first additive is present in an amount of 0.5wt% to 3wt%, preferably 1wt% to 3wt%, for example, 0.1wt%, 0.2wt%, 0.5wt%, 1.0wt%, 1.2wt%, 1.5wt%, 1.7wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.7wt%, 3wt%, or any point in the range of the two-point values.
The lone electron pair on the N atom in the N-containing group and the ortho-connected aromatic ring (such as benzene ring) in the first additive enable the first additive to have higher electron cloud density, and a small amount of the first additive is added into the electrolyte to show stronger Lewis basicity. The first additive can be combined with PF in electrolyte 5 Formation of complex (lithium hexafluorophosphate has poor thermal stability and is liable to undergo decomposition reaction: liPF) 6 →LiF+PF 5 Generated PF 5 The chemical property is active, and the electrolyte can react with proton impurities existing in trace amount in the electrolyte, so that the acidity and chromaticity of the electrolyte are quickly increased, the quality of the electrolyte is further deteriorated, the cycle performance and the high-temperature performance of the battery are reduced, and the acidity and the reactivity of the electrolyte are reduced, so that the increase of free acid of the electrolyte is inhibited; in addition, negative electron N atoms can be complexed with a positive electrode material (such as lithium cobaltate) to inhibit the electrode surface reactivity, reduce the oxidative decomposition of electrolyte at high temperature and effectively inhibit the thickness expansion of high-temperature storage; in addition, the first additive is easily oxidized and decomposed on the surface of the positive electrode in the electrolyte to form an interfacial film, so that the high-temperature cycle performance and the low-temperature discharge performance of the battery are further improved.
The electrolyte according to the present invention contains the second additive in an amount of 0.5wt% to 3wt%, preferably 1wt% to 3wt%, for example, 1.0wt%, 1.2wt%, 1.5wt%, 1.7wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.7wt%, 3wt% or any value in the range of the two values.
The second additive can form a layer of uniform and compact protective film on the surface of the positive electrode material, thereby reducing Li + The non-uniform embedding of the anode is realized, the corrosion of HF to the anode material is inhibited, the generation of cracks in particles of the anode material in the circulation process is avoided, the dissolution of transition metal elements at high temperature is reduced, and meanwhile, the second additive can be reduced on the surface of the anode material (the reduction potential is 1.5V vs Li + Li) to form compact stable SEI film, and reduce the oxidative decomposition of electrolyte on the surface of the anode material.
Further, the second additive is capable of decomposing into Li 2 SO 3 The components are equal, the impedance is lower, the resistance of lithium ions is reduced, and the low-temperature discharge performance of the battery is improved; the first additive and the second additive can be oxidized to form a film at the positive electrode, and the combination of the first additive and the second additive can further optimize the thermal stability and the oxidation resistance of the film, thereby improving the thermal shock and the high-temperature performance of the battery.
The electrolyte comprising the first additive and the second additive can improve the high-temperature storage performance and the thermal shock performance of the battery and also can give consideration to the high-temperature cycle performance and the low-temperature discharge performance of the battery.
The electrolyte according to the present invention is at least one electrolyte salt selected from the group consisting of lithium electrolyte salt, sodium electrolyte salt, zinc electrolyte salt, magnesium electrolyte salt and aluminum electrolyte salt.
As the electrolyte of the present invention, the electrolyte salt includes at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis-oxalato-phosphate, lithium tetrafluorooxalato-phosphate, lithium bis-oxalato-borate, lithium difluorooxalato-borate, lithium tetrafluoroborate, lithium difluorosulfonimide and lithium difluorosulfonimide.
As the electrolyte according to the present invention, the organic solvent includes at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, methylethyl carbonate, dimethyl carbonate, ethyl propionate, propyl propionate, ethyl acetate, ethyl n-butyrate, and γ -butyrolactone.
The electrolyte according to the present invention contains the electrolyte salt in an amount of 12.5wt% to 20wt%, for example, 12.5wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, or any point in the range of the two-point values.
According to an embodiment of the invention, the electrolyte is a high voltage electrolyte.
According to an embodiment of the present invention, the high voltage refers to a voltage of 4.45V or more.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
mixing electrolyte salt, an organic solvent and an additive to prepare the electrolyte;
wherein the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from 1,1' -sulfuryl diimidazole compounds.
The invention also provides a battery, which comprises the electrolyte.
According to an embodiment of the invention, the battery further comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate at intervals.
According to an embodiment of the present invention, the charge cut-off voltage of the battery is greater than or equal to 4.45V.
As an improvement of the battery of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode sheet including a positive electrode active material which is LiCoO 2 、LiNiO 2 、LiCo y M 1-y O 2 、LiNi y M 1- y O 2 、LiMn y M 1-y O 2 、LiNi 1-x-y-z Co x Mn y M z O 2 One or more than two of the components, wherein M is selected from Fe, co, ni, mn, mg, cu, zn, al,One or two of Sn, B, ga, cr, sr, V, ti, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x+y+z is more than or equal to 0 and less than or equal to 1.
As an improvement of the battery of the invention, the negative electrode sheet comprises a negative electrode current collector and a negative electrode membrane, the negative electrode membrane comprises a negative electrode active material, and the negative electrode active material is artificial graphite, natural graphite, lithium titanate, siO w Silicon-carbon composite material compounded with graphite 1<w<2。
The invention has the beneficial effects that:
the invention provides a high-voltage electrolyte and a battery containing the same, wherein the electrolyte comprises electrolyte salt, an organic solvent and an additive, and the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from 1,1' -sulfuryl diimidazole compounds.
According to the invention, through the synergistic effect of the first additive and the second additive, the film can be formed on the surface of the positive electrode, the direct contact of the electrode material and the electrolyte is avoided, the microstructure of the electrode material is stabilized, the dissolution of transition metal elements at high temperature is reduced, the SEI film can be formed on the surface of the negative electrode material, the reduction reaction of the solvent at the interface of the negative electrode is inhibited, and the high-temperature storage performance, the high-temperature circulation performance, the low-temperature discharge performance and the thermal shock performance of the battery under high voltage can be effectively improved.
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 illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first," "second," and the like are used for descriptive purposes only and are not indicative or implying relative importance.
Example 1
In a glove box filled with argon gas (oxygen content is less than or equal to 1ppm, water content is less than or equal to 1 ppm), ethylene carbonate, propylene carbonate and propyl propionate are mixed according to the mass ratio EC: PC: pp=2:1:7, and then 12.5wt% of lithium hexafluorophosphate (LiPF) based on the total mass of the electrolyte is slowly added into the mixed solution 6 ) Finally, 1.0wt% of the first additive and 1.5wt% of the second additive (the specific structural formula is shown in table 1) based on the total weight of the electrolyte are added, and the electrolyte of example 1 is obtained after uniform stirring.
Examples 2 to 17 and comparative examples 1 to 2
In examples 2 to 17 and comparative examples 1 to 2, the same as in example 1 was conducted except that the amounts and choices of the first additive and the second additive to be added to the electrolyte were as shown in Table 1.
Table 1 electrolyte compositions of examples and comparative examples
| First additive and content | Second additive and content | |
| Example 1 | 1wt% Compound 1 | 1.5wt% Compound 9 |
| Example 2 | 1wt% Compound 1 | 1.5wt% Compound 10 |
| Example 3 | 1wt% Compound 1 | 1.5wt% Compound 11 |
| Example 4 | 1wt% Compound 1 | 1.5wt% Compound 12 |
| Example 5 | 1wt% Compound 1 | 1.5wt% Compound 13 |
| Example 6 | 1wt% Compound 1 | 1.5wt% Compound 14 |
| Example 7 | 1wt% Compound 2 | 1.5wt% Compound 9 |
| Example 8 | 1wt% Compound 3 | 1.5wt% Compound 9 |
| Example 9 | 1wt% Compound 4 | 1.5wt% Compound 9 |
| Example 10 | 1wt% Compound 5 | 1.5wt% Compound 9 |
| Example 11 | 1wt% Compound 6 | 1.5wt% Compound 9 |
| Example 12 | 1wt% Compound 7 | 1.5wt% Compound 9 |
| Example 13 | 1wt% Compound 8 | 1.5wt% Compound 9 |
| Example 14 | 0.3wt% Compound 1 | 1.5wt% Compound 9 |
| Example 15 | 4wt% Compound 1 | 1.5wt% Compound 9 |
| Example 16 | 1wt% Compound 1 | 0.3wt% Compound 9 |
| Example 17 | 1wt% Compound 1 | 4wt% Compound 9 |
| Comparative example 1 | / | 1.5wt% Compound 9 |
| Comparative example 2 | 1wt% Compound 1 | / |
Test case
1. Assembling a battery: the electrolytes of examples 1 to 17 and comparative examples 1 to 2 described above were respectively used as electrolytes of batteries, and were assembled into a pouch-type battery,
a diaphragm: a PP separator;
positive pole piece: the positive electrode current collector is aluminum foil, and the positive electrode coating consists of lithium cobalt oxide, acetylene black and polyvinylidene fluoride PVDF in a mass ratio of 95:3:2;
negative pole piece: the negative electrode current collector is copper foil, and the negative electrode coating consists of artificial graphite, acetylene black and styrene butadiene rubber SBR in a mass ratio of 94:3:3.
After the positive electrode plate, the negative electrode plate and the PP diaphragm are sequentially overlapped, the electrolyte prepared in the examples 1-17 and the comparative examples 1-2 are respectively added to assemble soft package batteries, which are respectively marked as test batteries 1-17 and comparative batteries 1-2.
2. Electrochemical performance test: the blue electric charge and discharge test cabinet is adopted to test the electrochemical performance by the following test method:
(1) High temperature cycle performance test
High temperature cycle performance test: at 45 ℃, the battery after capacity division is charged to 4.50V according to a constant current and a constant voltage of 0.7C, the cut-off current is 0.05C, then the battery is discharged to 3.0V according to a constant current of 0.5C, the capacity retention rate at the 300 th week is calculated after 300 times of charge and discharge cycles according to the circulation, and the calculation formula is as follows:
cycle capacity retention at 300 weeks (%) = (cycle discharge capacity at 300 weeks/first cycle discharge capacity) ×100%.
(2) High temperature storage test at 60 ℃ for 14 days
Charging and discharging the battery at normal temperature for 1 time (4.50V-3.0V) at 0.5C, recording the discharge capacity C0 before the battery is stored, then charging the battery to 4.50V full state at constant current and constant voltage, testing the thickness d1 of the battery before the high-temperature storage (two diagonal lines of the battery are respectively connected through a straight line, and the intersection point of the two diagonal lines is a battery thickness test point) by using a vernier caliper, placing the battery into a 60 ℃ incubator for storage for 14 days, taking out the battery after the storage is completed, testing the thermal thickness d2 of the battery after the storage, and calculating the thickness expansion rate of the battery after the battery is stored at 60 ℃ for 14 days; after the battery is cooled for 24 hours at room temperature, the battery is discharged to 3.0V at a constant current of 0.5C, then the battery is charged to 4.50V at a constant current and constant voltage of 0.5C, the discharge capacity C1 and the charge capacity C2 of the battery after storage are recorded, and the residual capacity retention rate and the recovery capacity retention rate of the battery after storage at 60 ℃ for 14 days are calculated according to the following calculation formula:
thickness expansion ratio = (d 2-d 1)/d 1 x 100% after 14 days of storage at 60 ℃;
residual capacity retention = C1/C0 x 100% after 14 days storage at 60 ℃;
recovery capacity retention = C2/C0 x 100% after 14 days storage at 60 ℃.
(3) Low temperature discharge performance test
Discharging the battery with the capacity of 0.5C to 3.0V at the temperature of 25 ℃ and standing for 5min; charging to 4.50V at 0.2C, changing to 4.50V constant voltage charging when the voltage of the battery core reaches 4.50V until the charging current is less than or equal to the given cutoff current of 0.05C, and standing for 5min; transferring the fully charged core into a high-low temperature box, setting the temperature to-10 ℃, and standing for 120min after the temperature of the box reaches; then discharging at 0.2C to a final voltage of 3.0V, and standing for 5min; then the temperature of the high-low temperature box is adjusted to 25+/-3 ℃, and the box is left for 60 minutes after the temperature of the box is reached; then charging to 4.50V at 0.2C, and changing to 4.50V constant voltage charging when the voltage of the battery cell reaches 4.50V until the charging current is less than or equal to the given cutoff current of 0.05C; standing for 5min; the capacity retention rate of 3.0V discharge at-10 ℃ is calculated. The calculation formula is as follows:
-10 ℃ discharge 3.0V capacity retention (%) = (-10 ℃ discharge to 3.0V discharge capacity/25 ℃ discharge to 3.0V discharge capacity) ×100%.
(4) Thermal shock property
Discharging to 3.0V at a given current of 0.2C under ambient conditions of 25 ℃; standing for 5min; charging to 4.50V at a charging current of 0.2C, and changing to 4.50V constant voltage charging when the voltage of the battery cell reaches 4.50V until the charging current is less than or equal to a given cutoff current of 0.05C; placing the battery cell into an oven after the battery cell is placed for 1h, and raising the temperature of the oven to 130+/-2 ℃ at the speed of 5+/-2 ℃/min, and stopping after the battery cell is kept for 30min, wherein the judgment standard is that the battery cell is not fired and exploded, and the battery cell is pass.
Table 2 comparison of test results of electrolyte assembled batteries of examples 1 to 17 and comparative examples 1 to 2
From comparison of the test results of comparative examples 1 to 2 and examples 1 to 17 in Table 2, it is clear that:
the results of comparative examples 1-2 and examples 1-17 show that the synergistic effect of the first additive and the second additive not only inhibits the increase of the acidity of the electrolyte, but also forms interface protection films on the surfaces of the positive electrode and the negative electrode respectively, thereby being beneficial to improving the stability of the battery interface and further improving the high-temperature storage performance, the high-temperature cycle performance, the low-temperature discharge performance and the thermal shock performance of the battery under high voltage.
In addition, example 14 resulted in deterioration of thermal shock performance, high temperature cycle performance, low temperature discharge performance and high temperature storage performance of the battery due to formation of an incomplete interfacial film because the addition amount of the first additive was small. Example 15 because the first additive was added in a large amount, the interfacial film was too thick and the resistance was large, resulting in a decrease in the high temperature cycle performance, low temperature discharge performance and high temperature storage performance of the battery. Example 16 because the amount of the second additive compound added was small, the thermal shock property, the high temperature cycle property and the high temperature storage property were deteriorated. Example 17 the resistance was increased and the gas production in high temperature storage was increased because the amount of the second additive added was increased.
Comparative example 1 remarkably deteriorated thermal shock performance, high temperature cycle performance and low temperature discharge performance of the battery because it did not contain the first additive. Comparative example 2 was not contained with the second additive, resulting in significant deterioration of thermal shock performance, high temperature cycle performance and low temperature discharge performance of the battery.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
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, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. An electrolyte comprising an electrolyte salt, an organic solvent and an additive, wherein the additive comprises a first additive and a second additive;
the first additive is selected from at least one of a compound shown in a formula I or a compound shown in a formula II:
in the formula I and the formula II, R 1 Selected from substituted or unsubstituted aryl, if substituted aryl, the substituents are selected from alkyl, haloalkyl or halogen;
in the formula I, R 2 And R is 3 The same or different, independently of one another, from alkyl groups;
in the formula II, the N-containing ring group is a saturated ring group containing at least one N atom;
the second additive is at least one selected from compounds shown in a formula III:
in formula III, n 1 0, 1, 2 or 3; n is n 2 0, 1, 2 or 3;
R 4 and R is 5 Identical or different, independently of one another, from H, halogen, cyano, unsubstituted or optionally substituted by one, two or more R' a Substituted with the following groups: c (C) 1-6 Alkyl, C 2-6 Alkenyl, C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, sulfo (-SO) 3 H)；
Each R' a The same or different, independently of one another, are selected from halogen, C 1-6 An alkyl group.
2. The electrolyte of claim 1 wherein in formulas I and II, R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and the substituents are selected from the group consisting of C 1-6 Alkyl, halogenated C 1-6 Alkyl or halogen;
and/or, in formula I, R 2 And R is 3 Identical or different, independently of one another, from C 1-6 An alkyl group.
3. The electrolyte of claim 2 wherein in formula II the N-ring containing group is unsubstituted or optionally substituted with one or more R containing at least one N atom a Substituted saturated cyclic groups;
R a is halogen, -CN, -NO 2 、-NH 2 、-CO-NH 2 Unsubstituted or optionally substituted by one or more R b Substituted as follows: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl;
R b is halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl groups.
4. The electrolyte of claim 3 wherein in formula II, the N-ring containing group is selected from one of the N-ring containing groups shown below:
wherein, represent the connection.
5. The electrolyte according to any one of claims 1 to 4, wherein the first additive is selected from at least one of the following compounds 1 to 8:
6. the electrolyte according to any one of claims 1 to 4, wherein the second additive is selected from at least one of compounds 9 to 14:
7. the electrolyte according to any one of claims 1 to 4, wherein the mass of the first additive is 0.5wt% to 3wt% of the total mass of the electrolyte;
and/or the mass of the second additive accounts for 0.5-3 wt% of the total mass of the electrolyte.
8. A battery, wherein the battery comprises the electrolyte of any one of claims 1-7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210039436.6A CN114464883B (en) | 2022-01-13 | 2022-01-13 | High-voltage electrolyte and battery containing same |
| PCT/CN2023/071704 WO2023134691A1 (en) | 2022-01-13 | 2023-01-10 | High-voltage electrolyte and battery containing electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210039436.6A CN114464883B (en) | 2022-01-13 | 2022-01-13 | High-voltage electrolyte and battery containing same |
Publications (2)
| Publication Number | Publication Date |
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| CN114464883A CN114464883A (en) | 2022-05-10 |
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| JP2002280063A (en) * | 2001-03-15 | 2002-09-27 | Sony Corp | Electrolyte and battery |
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| CN112928328A (en) * | 2019-12-06 | 2021-06-08 | 孚能科技(赣州)股份有限公司 | Lithium ion battery electrolyte containing silane sulfonamide compound and lithium ion secondary battery |
| CN111668542A (en) * | 2020-06-30 | 2020-09-15 | 上海枭源能源科技有限公司 | Non-aqueous electrolyte containing halogenated benzene sulfonamide and lithium secondary battery |
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| CN114464883A (en) | 2022-05-10 |
| WO2023134691A1 (en) | 2023-07-20 |
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