CN113161612A - Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same - Google Patents
Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN113161612A CN113161612A CN202110350949.4A CN202110350949A CN113161612A CN 113161612 A CN113161612 A CN 113161612A CN 202110350949 A CN202110350949 A CN 202110350949A CN 113161612 A CN113161612 A CN 113161612A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium
- solvent
- ion battery
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- 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
-
- 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 relates to a non-aqueous electrolyte for a lithium ion battery and the lithium ion battery containing the same. The non-aqueous electrolyte comprises an organic solvent, lithium sulfonimide salt and an additive for inhibiting negative electrode stripping, wherein the organic solvent is a mixture of a phosphate solvent and a second ester solvent, the lithium sulfonimide salt accounts for 20-45 wt% of the non-aqueous electrolyte, the additive accounts for 0.3-20 wt%, the organic solvent accounts for 50-75 wt%, the phosphate solvent accounts for 50-90% of the organic solvent by volume, and the second ester solvent accounts for 10-30% of the organic solvent by volume. The second ester solvent has a structure represented by the following formula (I): in the formula (I), R1Selected from alkyl or alkoxy groups having 1 to 4 carbon atoms, R2 is selected from the group consisting ofAlkyl having 1 to 4 carbon atoms, or, R1And R2Bonded to each other and form a ring having 3 to 6 carbon atoms together with the adjacent carbonyl carbon atoms and oxygen atoms, and the atoms bonded to the carbonyl carbon atoms in the ring are all oxygen.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a non-aqueous electrolyte for a lithium ion battery and the lithium ion battery comprising the same.
Background
The use of traditional fossil fuels releases a large amount of carbon dioxide and harmful gases such as sulfide, nitride and dust, causing greenhouse effect and polluting the environment, and the development and utilization of renewable clean energy sources are imperative as the traditional fossil fuels are gradually exhausted. The clean energy comprises water energy, solar energy, wind energy, tidal energy, nuclear energy and the like, and belongs to renewable energy. The energy sources can be utilized in a mode of electric energy-energy in other forms-electric energy through intermediate conversion, namely, energy storage equipment is utilized, and a lithium ion battery in an energy storage device is paid much attention due to the advantages of high voltage, high energy density, long service life, high safety and the like, so that the lithium ion battery is rapidly developed in the application fields of portable electronic products, large-scale power supplies and energy storage power stations.
The safety problem of lithium ion batteries is always concerned, however, most of the current lithium ion batteries use carbonate organic electrolyte which is very easy to burn, and the batteries may be burnt or even exploded due to overcharge, overdischarge, overheating and the like. In some high and new technology fields, such as airplanes, satellites and the like, a completely non-combustible electrolyte is needed.
An electrolyte for a lithium ion battery generally consists of a lithium salt, an organic solvent dissolving the lithium salt, and a functional additive, wherein proper selection of these components is very important to improve the electrochemical performance of the battery. In the prior art, a non-combustible phosphate solvent is generally used as an organic solvent for dissolving lithium salt to improve the safety performance of the battery, but the phosphate-based solvent has a stripping effect on a negative electrode, is poor in compatibility with a positive electrode and a negative electrode, is easy to cause battery failure, and is poor in cycle performance.
Disclosure of Invention
Accordingly, there is a need for a nonaqueous electrolyte for a lithium ion battery, which has both good incombustibility and good cycle performance, and a lithium ion battery comprising the same.
In one aspect of the present invention, there is provided a nonaqueous electrolyte for a lithium ion battery, including an organic solvent, a lithium sulfonimide salt, and an additive for inhibiting negative electrode exfoliation, wherein the organic solvent is a mixture of a phosphate solvent and a second ester solvent, and the second ester solvent is a carbonate solvent and/or a fatty ester solvent having a structure represented by the following formula (i):
in the formula (I), R1Selected from alkyl or alkoxy groups having 1 to 4 carbon atoms, R2Selected from alkyl groups having 1 to 4 carbon atoms, or, R1And R2Bonding with each other and forming a ring with 3-6 carbon atoms together with adjacent carbonyl carbon atoms and oxygen atoms, wherein the atoms bonded with the carbonyl carbon atoms in the ring are all oxygen;
in the non-aqueous electrolyte, the content of the lithium sulfonimide salt is 20-45 wt%, the content of the additive is 0.3-20 wt%, and the content of the organic solvent is 50-75 wt%, wherein the phosphate solvent accounts for 50-90% of the volume of the organic solvent, and the second ester solvent accounts for 10-30% of the volume of the organic solvent.
In another aspect of the invention, the invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and the nonaqueous electrolyte for the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the non-aqueous electrolyte for the lithium ion battery provided by the invention is characterized in that a second ester solvent and a phosphate ester solvent of a specific type are matched with each other in a specific ratio to improve the wettability of the electrolyte to an electrode and a diaphragm, and a specific amount of additive for inhibiting negative electrode stripping and sulfonyl imide salt are matched to construct a novel non-combustible electrolyte system. The lithium ion battery using the electrolyte has good non-combustibility, cycle performance and rate capability.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The embodiment of the invention provides a nonaqueous electrolyte for a lithium ion battery, which comprises an organic solvent, lithium sulfonimide salt and an additive for inhibiting negative electrode stripping, wherein the organic solvent comprises a mixture of a phosphate solvent and a second ester solvent, and the second ester solvent is a carbonate solvent and/or a fatty ester solvent with a structure shown in a formula (I):
in the formula (I), R1Selected from alkyl or alkoxy groups having 1 to 4 carbon atoms, R2Selected from the range of 1 &Alkyl of 4 carbon atoms, or, R1And R2Bonding with each other and forming a ring with 3-6 carbon atoms together with adjacent carbonyl carbon atoms and oxygen atoms, wherein the atoms bonded with the carbonyl carbon atoms in the ring are all oxygen;
in the non-aqueous electrolyte, the content of the lithium sulfonimide salt is 20-45 wt%, the content of the additive is 0.3-20 wt%, and the content of the organic solvent is 50-75 wt%, wherein the phosphate solvent accounts for 50-90% of the volume of the organic solvent, and the second ester solvent accounts for 10-30% of the volume of the organic solvent.
The phosphate organic solvent has flame retardancy, but at the same time, the phosphate organic solvent is easy to generate a co-intercalation effect with lithium ions, so that a negative electrode is peeled off, and the phosphate organic solvent has poor wettability and poor compatibility with a battery as a solvent. According to the invention, a second ester solvent and a phosphate ester solvent of a specific type are selected to be matched with each other in a specific proportion, so that the wettability of the electrolyte to an electrode and a diaphragm is improved, and a novel non-combustible electrolyte system is constructed by matching a specific amount of additive for inhibiting the stripping of a negative electrode and sulfimide salt. The electrolyte system has good incombustibility, and compared with the incombustible electrolyte in the prior art, the electrolyte has better electrochemical performance, and a lithium ion battery using the electrolyte has good incombustibility, cycle performance and rate capability.
The lithium salt of sulfonimide may be any lithium salt of sulfonimide commonly used in the art, and may include, for example, but not limited to, lithium bis (fluorosulfonyl) imide (F)2LiNO4S2) Lithium bis (trifluoromethanesulfonyl) imide (C)2F6LiNO4S2) 1,1,2,2,3, 3-hexafluoropropane-1, 3-disulfonylimide lithium (C)3F6LiNO4S2) Bis (nonafluorobutylsulfonyl) imide lithium (C)8F18LiNO4S2) Lithium bis (1,1,1,3,3, 3-hexafluoroisopropoxysulfonyl) imide (C)6F12H2LiNO6S2) One or more of (a).
At one endIn some preferred embodiments, the lithium salt of sulfonimide is selected from lithium bis (fluorosulfonyl) imide (F)2LiNO4S2) Lithium bis (trifluoromethanesulfonyl) imide (C)2F6LiNO4S2) 1,1,2,2,3, 3-hexafluoropropane-1, 3-disulfonylimide lithium (C)3F6LiNO4S2) Bis (nonafluorobutylsulfonyl) imide lithium (C)8F18LiNO4S2) Any one of them.
In some more preferred embodiments, the lithium salt of sulfonimide is selected from lithium bis (trifluoromethanesulfonyl) imide or lithium bis (fluorosulfonyl) imide.
The content of the lithium sulfonimide salt in the nonaqueous electrolytic solution is 20 to 45 wt%, and any value within this range may be included, for example, but not limited to, 25%, 30%, 35%, and 40%. The lithium sulfonimide salt concentration within this range may make the impregnation of the electrolyte and the synergy with other components more excellent.
The organic solvent is a mixture of a phosphate ester solvent and a second ester solvent, and the second ester solvent is a carbonate ester solvent and/or a fatty ester solvent with a structure shown in the following formula (I):
in some embodiments, in formula (I), R1Selected from alkyl or alkoxy groups having 1 to 4 carbon atoms, R2Selected from alkyl groups having 1 to 4 carbon atoms.
In other embodiments, R1And R2Bonded to each other and form a ring having 3 to 6 carbon atoms together with the adjacent carbonyl carbon atoms and oxygen atoms, and the atoms bonded to the carbonyl carbon atoms in the ring are all oxygen.
Preferably, the carbonate-based solvent is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
Preferably, the fatty ester-based solvent is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate. .
The phosphate ester solvent has a structure represented by the following formulae (II-1) and (II-2):
in the formulae (II-1) and (II-2), R4～R6Each independently selected from an alkyl group having 1 to 10 carbon atoms or an unsaturated hydrocarbon group. The substance is used as a solvent, and the flame retardance of the electrolyte can be improved.
Alternatively, R4～R6Each independently selected from alkyl, haloalkyl, unsaturated hydrocarbon group or halogenated unsaturated hydrocarbon group having 1 to 6 carbon atoms. In particular, R4～R6Each independently selected from an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, an unsaturated hydrocarbon group or a halogenated unsaturated hydrocarbon group.
Specifically, the phosphate-based solvent may be selected from, but is not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trioctyl phosphate, dimethyl phosphate, dibutyl phosphate, triallyl phosphate, trimethyl phosphite, triethyl phosphite, dibutyl phosphite, triisopropyl phosphite, tris (2-chloroethyl) phosphate, tris (1-chloro-2-propyl) phosphate, trichloropropyl phosphite, tris (2, 3-dichloropropyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate, tetraisopropyl methylenediphosphate, tetraethyl methylenediphosphate, tetramethylmethylenediphosphate, di-tert-butyl chloromethyl phosphate, tris (2,2, 2-trifluoroethyl) phosphite, tri (2,2, 2-trifluoroethyl) phosphite, One or more of bis (2,2, 2-trifluoroethyl) methyl phosphate, tris (2-chloroethyl) phosphite, tris (1,1,1,3,3, 3-hexafluoro-2-propyl) phosphate, tris (1,1,1,3,3, 3-hexafluoro-2-propyl) phosphite, dimethyl-vinyl phosphate, diethyl vinyl phosphate, dimethyl vinyl phosphate, diallyl chloride phosphite, tetraethylfluoromethylene diphosphate and tetrakis (2-chloroethyl) ethylene diphosphate.
Preferably, the phosphate-based solvent is selected from one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trioctyl phosphate, dimethyl phosphate, dibutyl phosphate, triallyl phosphate, trimethyl phosphite, triethyl phosphite, dibutyl phosphite, isopropyl phosphite, dimethyl-vinyl phosphate, diethyl vinyl phosphate, and dimethyl vinyl phosphate. The phosphate ester has better compatibility as an organic solvent and other components, particularly has better solubility to lithium sulfonimide, and is favorable for improving the wettability and electrochemical performance of the electrolyte.
Further preferably, the phosphate-based solvent is selected from trimethyl phosphate, triethyl phosphate and/or trimethyl phosphite. Trimethyl phosphate, triethyl phosphate and/or trimethyl phosphite as solvent and carbonic acid/fatty ester solvent have better synergistic effect, so that the electrolyte has better wettability.
In some embodiments, the organic solvent further comprises a fluorinated solvent selected from fluoroethers and/or fluorinated carbonates having a degree of fluorine substitution of 50% or more and a number of carbon atoms of 2,3, 4, 5, or 6. The fluoro-solvent has good wettability and flame retardance, has general solubility, and can be matched with a phosphate solvent and a carbonic acid/fatty ester solvent in a synergistic manner, so that the compatibility of the flame-retardant electrolyte and positive and negative electrodes can be better improved, and the impedance can be reduced. In addition, the fluoro solvent can also act synergistically with the additive to form a more stable interfacial film at the positive and negative electrode interfaces.
Preferably, the fluorinated solvent is selected from one or more of 1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether, 1- (2,2, 2-trifluoroethoxy) -1,1,2, 2-tetrafluoroethane, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 3,3, 3-trifluoropropylene carbonate and bis (2,2, 2-trifluoroethyl) carbonate.
The content of the organic solvent in the nonaqueous electrolytic solution may be any value between 50 wt% and 75 wt%, and may include, for example, but is not limited to, 55 wt%, 60 wt%, 65 wt%, and 70 wt%.
The volume percentage of the phosphate ester solvent in the organic solvent is any value between 50% and 90%, such as 55%, 60%, 65%, 70%, 75%, 80%.
The volume percentage of the second ester solvent in the organic solvent is any value between 10% and 30%, for example, 15%, 20%, 25%.
The volume percentage of the fluorinated solvent in the organic solvent is any value between 0.5% and 30%, such as 1%, 5%, 10%, 15%, 20%, 25%.
In some embodiments, the organic solvent is a mixture of a phosphate ester solvent and a second ester solvent, and the volume ratio of the phosphate ester solvent to the second ester solvent may be (7-9): any ratio of (1) - (3) may be, for example, 8:2, 8.5:1.5, 7.5: 2.5. Preferably, the content of the second ester solvent in the organic solvent is more than 10%.
In other embodiments, the organic solvent is a mixture of a phosphate ester solvent, a second ester solvent and a fluorinated solvent, and the volume ratio of the phosphate ester solvent to the second ester solvent to the fluorinated solvent may be (5-8.95): (1-3): the ratio of (0.05-3) may be, for example, 5:3:2, 6:3:1, 7:2:1, 8:1:1, 8.95:1: 0.05. Preferably, the content of the phosphate ester solvent in the organic solvent is less than or equal to 80%. More preferably, the volume ratio of the phosphate ester solvent, the second ester solvent and the fluorinated solvent is 5:3:2, 6:3:1, 7:2:1, 8:1: 1.
The additive for inhibiting the negative electrode from peeling off can be selected from one or more of phosphorus-containing additives, boron-containing additives, phosphorus-nitrogen additives, fluorotriazine additives, negative electrode reducing agents, silicon-based phosphate esters and aluminum current collector protective agents.
The phosphorus-containing additive may be selected from one or more of lithium difluorophosphate, lithium difluorooxalate phosphate, lithium tetrafluorooxalate phosphate, dilithium acetyl phosphate, and dilithium carbamyl phosphate. Preferably, the phosphorus-containing additive is lithium difluorophosphate and/or dilithium acetyl phosphate.
The boron-containing additive may be selected from one or more of lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, and lithium trifluoro (trifluoromethyl) borate. Preferably, the boron-containing additive is lithium tetrafluoroborate, lithium difluorooxalate borate and/or lithium bis-oxalate borate.
The content of the phosphorus-containing additive or the boron-containing additive in the nonaqueous electrolytic solution may be any value between 0.1 wt% and 5 wt%, and may include, for example, but is not limited to, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and 4.5 wt%.
The phosphorus nitrogen additive has a structure represented by the following formula (A):
in the formula (A), Ra、Rb、RcEach independently selected from substituted or unsubstituted alkylene groups having 2 to 10 carbon atoms.
Preferably, in formula (A), Ra、Rb、RcEach independently selected from substituted or unsubstituted alkylene groups having 3 to 7 carbon atoms.
More preferably, in formula (A), Ra、Rb、RcAre each independently selected from-CR1H-CR2H-CR3H- (wherein, R)1、R2And R3Each independently selected from hydrogen or alkyl having 1 to 2 carbon atoms), -CR4H-CR5H-CR6H-CR7H- (wherein, R)4、R5、R6And R7Each independently selected from hydrogen or alkyl having 1 to 2 carbon atoms) or-CR8H-CR9H-CR10H-CR11H-CR12H- (wherein, R)8、R9、R10、R11And R12Each independently selected from hydrogen or an alkyl group having 1 to 2 carbon atoms).
Further preferably, the phosphorus nitrogen additive has a structure represented by the following formula (a):
in the nonaqueous electrolytic solution, the content of the phosphorus-nitrogen additive may be 0.01 to 5 wt%, and any value within this range may be included, for example, but not limited to, 0.05mol/L, 1.0mol/L, 1.5mol/L2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4mol/L, and 4.5 mol/L. The phosphorus-nitrogen additive can play a better synergistic effect with other components in the range. Preferably, the content of the phosphorus-nitrogen additive is 3 wt% -5 wt%, and the phosphorus-nitrogen additive can better complex transition metal ions in the electrolyte within the range, so that the oxidative decomposition and gas generation of the electrolyte are inhibited, and the cycle performance of the lithium ion battery is improved. More preferably, the phosphorus nitrogen additive is present in an amount of 5 wt%.
The fluorotriazine additive has a structure represented by the following formula (B):
in the formula (I), Rd、Re、RfEach independently selected from F or fluoroalkyl having 1 to 10 carbon atoms.
The fluoroalkyl group means an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The fluoroalkyl group may be a monofluoroalkyl group, a polyfluoroalkyl group, or a perfluoroalkyl group. By monofluoroalkyl is meant an alkyl group in which only one hydrogen atom is replaced by a fluorine atom and the remaining hydrogen atoms are unsubstituted. The polyfluoroalkyl group means an alkyl group in which a plurality of hydrogen atoms are substituted with fluorine atoms and the remaining hydrogen atoms are unsubstituted. By perfluoroalkyl is meant that all hydrogen atoms in the alkyl group are replaced by fluorine atoms.
Preferably, in the formula (B), Rd、Re、RfEach independently selected from F, polyfluoroalkyl or perfluoroalkyl having 1 to 10 carbon atoms. Specific examples include, but are not limited to, trimerizationOne or more of flucyanogen, 2,4, 6-tris (heptafluoropropyl) -1,3, 5-triazine, 2,4, 6-tris (pentafluoroethyl) s-triazine, 2,4, 6-tris (trifluoromethyl) -1,3, 5-triazine, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, 2,4, 6-tris (difluoromethyl) -1,3, 5-triazine, 2,4, 6-tris (trifluoromethyl) -1,3, 5-triazine, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine and 2,4, 6-tris (heptafluoropropyl) -1,3, 5-triazine.
More preferably, in the formula (B), Rd、Re、RfEach independently selected from F or a perfluoroalkyl group having 1 to 3 carbon atoms. Specific examples include, but are not limited to, one or more of melamine, 2,4, 6-tris (heptafluoropropyl) -1,3, 5-triazine, 2,4, 6-tris (pentafluoroethyl) s-triazine, 2,4, 6-tris (trifluoromethyl) -1,3, 5-triazine.
The amount of the fluorotriazine additive in the nonaqueous electrolytic solution may be 0.01 to 5 wt%, and any amount within this range may be included, for example, but not limited to, 0.05mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4mol/L, and 4.5 mol/L. The fluorotriazine additive can exert better synergistic effect with other components in the range. Preferably, the content of the fluorotriazine additive is 1 wt% -3 wt%, and the fluorotriazine additive can better complex transition metal ions in the electrolyte within the range, so that the oxidative decomposition and gas generation of the electrolyte are inhibited, and the cycle performance of the lithium ion battery is improved.
The negative electrode reducing agent may be selected from one or more of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, ethylene sulfate, ethylene sulfite, ethylene sulfate, ethylene carbonate, propylene sulfate, 1, 4-butane sultone, 1, 3-propane sultone, and tris (trimethylsilyl) borate. Preferably, the negative electrode reducing agent is any one of vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate and 1, 3-propane sultone.
The content of the negative electrode reducing agent in the nonaqueous electrolytic solution may be any value between 0.1 wt% and 3 wt%, and may include, for example, but is not limited to, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, and 2.5 wt%.
The silyl phosphate may be selected from one or more of tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphate, bis (trimethylsilyl) phosphite and acetyl bis (trimethylsilyl) trifluorophosphate. Preferably, the silicon-based phosphate is acetyl bis (trimethylsilyl) trifluorophosphate.
The content of the silicon-based phosphate ester in the nonaqueous electrolytic solution may be any value between 0.1 wt% and 3 wt%, and may include, for example, but is not limited to, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, and 2.5 wt%.
The aluminum current collector protectant may be selected from LiClO4、LiAsF6、LiPF6、LiBF4One or more of LiBOB, LiDFOB and nitrile compounds.
The nitrile compound may be selected from one or more of succinonitrile, adiponitrile, glutaronitrile, suberonitrile, sebaconitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-pentanetrimethylcarbonitrile, p-fluorobenzonitrile, p-methylbenzonitrile, 2-fluoroadiponitrile, 2-difluorosuccinonitrile, tricyanobenzene, acrylonitrile, crotononitrile, trans-butenenitrile, trans-hexenedionitrile, 1, 2-di (cyanoethoxy) ethane, 1,2, 3-tris (cyanoethoxy) propane, bis (cyanoethyl) sulfone, 3- (trimethylsiloxy) propionitrile, pentafluoroethoxy tricyclotriphosphazene, and hexamethoxycyclotriphosphazene.
Preferably, the aluminum current collector protectant is selected from LiClO4、LiAsF6、LiPF6One or more of succinonitrile, adiponitrile, and combinations thereof.
The content of the silicon-based phosphate in the nonaqueous electrolytic solution can be any value between 0.1 wt% and 5 wt%, and for example, but not limited to, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4mol/L, 4.5mol/L can also be included.
In some preferred embodiments, the additive for inhibiting the anode peeling is a phosphorus-containing additive, an anode reducing agent, and an aluminum current collector protectant.
In other preferred embodiments, the additive for inhibiting the peeling of the negative electrode is a boron-containing additive, a negative electrode reducing agent, and an aluminum current collector protective agent.
In another aspect of the invention, a lithium ion battery is also provided, which comprises a positive electrode, a negative electrode and the nonaqueous electrolyte for the lithium ion battery.
In one embodiment, the positive electrode of the lithium ion battery comprises an aluminum current collector. The non-aqueous electrolyte for the lithium ion battery has a better effect of improving the cycle performance of the lithium ion battery with the anode current collector being an aluminum current collector.
The lithium ion battery of the present invention may be prepared and used according to a conventional method known in the art. The preparation method of the lithium ion battery of the invention is specifically described as follows.
(1) Positive electrode
The preparation method of the positive electrode can be as follows: a positive electrode current collector is coated with a positive electrode slurry including a positive electrode active material, a binder, a conductive agent, and a solvent, and then the coated positive electrode current collector is dried and rolled.
The positive electrode current collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, or the like may be used.
In a preferred embodiment, the positive electrode current collector is selected from aluminum current collectors.
The positive electrode active material is a compound that reversibly intercalates and deintercalates lithium. The cathode active material according to the present invention may be any cathode active material known in the art, including, but not limited to, carbon-coated lithium iron phosphate, lithium cobaltate, doped and/or surface-modified lithium cobaltate, layered lithium-rich manganese oxide, doped and/or surface-modified lithium-rich manganese oxide, spinel lithium manganese oxide, doped and/or surface-modified spinel lithium manganese oxide, spinel lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Doped and/or surface-modified spinels (LiNi)0.5Mn1.5O4) Layered lithium nickel oxides, doped and/or surface-modified lithium nickel oxidesOne or more of them.
The content of the positive electrode active material may be 80 wt% to 99 wt%, for example, 90 wt% to 99 wt%, based on the total weight of solid components in the positive electrode slurry. In the case where the amount of the positive electrode active material is 80 wt% or less, the capacity may be reduced due to a reduction in energy density.
The binder is a component that contributes to adhesion between the active material and the conductive agent and adhesion to the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of solid components in the positive electrode slurry. Examples of the binder may include, but are not limited to, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, various copolymers, and the like.
The conductive agent is a material that provides conductivity without causing adverse chemical changes in the battery, and may be added in an amount of 1 to 20 wt% based on the total weight of solid components in the positive electrode slurry. Examples of the conductive agent may include, but are not limited to, carbon powder such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite or graphite having a well-grown crystal structure; conductive fibers, such as carbon fibers or metal fibers; conductive powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
The solvent may include: water or an organic solvent such as N-methyl-2-pyrrolidone (NMP) and alcohol, and may be used in such an amount that a desired viscosity is obtained when a cathode active material and optionally a binder and a conductive agent are included. For example, the solvent may be contained in an amount such that the concentration of the solid component in the slurry containing the positive electrode active material and optionally the binder and the conductive agent is 10 wt% to 60 wt%, for example, 20 wt% to 50 wt%.
(2) Negative electrode
The preparation method of the negative electrode can be as follows: a cathode current collector is coated with a cathode slurry including a cathode active material, a binder, a conductive agent, and a solvent, and then the coated cathode current collector is dried and rolled.
The negative electrode current collector generally has a thickness of 3 to 500 μm. The negative electrode collector is not particularly limited as long as it has high conductivity without causing adverse chemical changes in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, or copper or stainless steel surface-treated with one of carbon, nickel, titanium, or silver, or an aluminum-cadmium alloy, or the like may be used. In addition, the negative electrode current collector may have various shapes such as a rod shape, a plate shape, a sheet shape, and a foil shape, like the positive electrode current collector.
The negative active material of the present invention may be any negative active material known in the art, including, for example, but not limited to, metallic lithium, graphite, natural graphite, artificial graphite, hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Tin-based composite material, spinel-structured lithiated TiO2, Li4Ti5O12One or more of Li-Al alloy, silicon, Li-Si alloy, Li-Si-O alloy, silicon-based composite material and tin-silicon composite material.
The content of the anode active material may be 80 wt% to 99 wt% based on the total weight of solid components in the anode slurry.
Similar to the binder, the conductive agent and the solvent in the positive electrode, the binder, the conductive agent and the solvent in the negative electrode are added in amounts calculated based on the total weight of the solid components in the negative electrode slurry, and the specific contents, functions and kinds thereof are the same as those of the binder, the conductive agent and the solvent in the positive electrode, and are not described herein again. The skilled person can select a suitable binder, conductive agent and solvent for the negative electrode according to actual requirements.
(3) Diaphragm
A separator used in a general lithium ion battery is selected, for example, a porous polymer film prepared from polyolefin polymers such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, an ethylene/methacrylate copolymer and the like is selected, and the porous polymer film can be used alone as a separator or laminated together as a separator included in the lithium ion battery of the present invention, and a non-woven fabric formed of polyester fibers, aramid fibers, glass fibers and the like can also be used; and a base film formed by adhering ceramic fine particles such as silica, alumina, and titania to the surfaces thereof.
The following are specific examples which are not intended to limit the invention in any way. The reagents and apparatus of the following examples are all well known in the art. The following english abbreviations have the following meanings: EC (ethylene carbonate), PC (propylene carbonate), DEC (diethyl carbonate), EMC (ethyl methyl carbonate).
Lithium bis (trifluoromethanesulfonyl) imide CAS no: 90076-65-6; lithium bis (fluorosulfonyl) imide CAS no: 171611-11-3; fluoroethylene carbonate CAS No.: 114435-02-8.
Example 1
1. Preparation of non-aqueous electrolyte for lithium ion battery
In a glove box filled with argon, 3g of lithium bis (oxalato) borate, 3g of vinylene carbonate, and 0.1g of LiClO4And 20g of lithium bis (fluorosulfonyl) imide was added to 73.9g of a nonaqueous organic solvent (trimethyl phosphate and propylene carbonate in a volume ratio of 7: 3), and stirred until completely dissolved, to prepare a nonaqueous electrolytic solution for a lithium ion battery.
2. Preparation of lithium ion battery
The anode active material LiFePO is added4Adding the positive conductive additive carbon black and the positive binder polyvinylidene fluoride (PVDF) into NMP according to the mass ratio of 92:5:3, and uniformly mixing to prepare positive slurry (the solid content is 60 wt%). Coating the slurry on aluminum foil current collector (coating thickness is 15 μm), drying, cold pressing, and cutting into particles with diameter of 15 μm
The round piece is used as a positive pole piece and is placed in a glove box.
Adding graphite serving as a negative electrode active material, carbon black serving as a negative electrode conductive additive, carboxymethyl cellulose (CMC) serving as a negative electrode binder and a copolymer (SBR) of styrene and butadiene into water according to a mass ratio of 93:2:2:3, and uniformly mixing to prepare negative electrode slurry(solid content 60 wt%). Coating the negative electrode slurry on a copper foil current collector (coating thickness is 15 μm), drying, cold pressing, and cutting into a sheet with a diameter of
The wafer is used as a negative pole piece and is placed in a glove box.
Polyethylene (PE) is used as a base film (12 mu m), and a nano aluminum oxide coating (2 mu m) is coated on the two sides of the base film to be used as a diaphragm.
And placing the positive pole piece, the diaphragm and the negative pole piece in sequence, injecting the prepared non-aqueous electrolyte for the lithium ion battery, packaging and assembling into a button cell with the model number of CR 2032.
Example 2
The preparation method is basically the same as that of the example 1, except that the non-aqueous organic solvent is trimethyl phosphate and propylene carbonate in a volume ratio of 8: 2.
Example 3
The preparation method is basically the same as that of the example 1, except that the non-aqueous organic solvent is trimethyl phosphate and propylene carbonate in a volume ratio of 9: 1.
Example 4
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 0.1g of lithium bis (oxalato) borate, 0.1g of vinylene carbonate, 1g of LiAsF6And 22.8g lithium bis (fluorosulfonyl) imide was added to 75g of a nonaqueous organic solvent (trimethyl phosphate, butenyl carbonate, and 1- (2,2, 2-trifluoroethoxy) -1,1,2, 2-tetrafluoroethane in a volume ratio of 8.95:1: 0.05).
Example 5
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 1.5g of lithium tetrafluoroborate, 0.1g of ethylene sulfate and 5g of LiPF6And 30g of lithium 1,1,2,2,3, 3-hexafluoropropane-1, 3-disulfonimide were added to 63.6g of a nonaqueous organic solvent (trimethyl phosphate, dimethyl carbonate and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether in a volume ratio of 8:1: 1).
Example 6
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 5g of lithium bis (oxalato) borate, 3g of fluoroethylene carbonate, 5g of succinonitrile and 38g of lithium bis (fluorosulfonyl) imide were added to 50g of a non-aqueous organic solvent (trimethyl phosphate, ethyl methyl carbonate and propylene 3,3, 3-trifluorocarbonate in a volume ratio of 7:2: 1.
Example 7
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 0.5g of lithium difluorophosphate, 1g of vinylene carbonate, 2g of p-methylbenzonitrile and 45g of lithium bis (trifluoromethanesulfonyl) imide were added to 51.5g of a nonaqueous organic solvent (trimethyl phosphate, ethyl acetate and bis (2,2, 2-trifluoroethyl) carbonate in a volume ratio of 6:3: 1).
Example 8
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 0.5g of lithium difluorophosphate, 1g of vinylene carbonate, 2g of p-methylbenzonitrile and 36.5g of lithium bis (trifluoromethanesulfonyl) imide were added to 60g of a nonaqueous organic solvent (trimethyl phosphate, ethyl acetate and 1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether in a volume ratio of 5:3: 2).
Example 9
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 0.5g of lithium difluorophosphate, 1g of vinylene carbonate, 2g of p-methylbenzonitrile and 36.5g of lithium bis (trifluoromethanesulfonyl) imide were added to 60g of a nonaqueous organic solvent (trimethyl phosphate, ethyl acetate and propylene 3,3, 3-trifluorocarbonate in a volume ratio of 6:3: 1).
Comparative example 1
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows:
in a glove box filled with argon, 40g of lithium bis (trifluoromethanesulfonyl) imide were added to 60g of a non-aqueous organic solvent (trimethyl phosphate) and stirred until it was completely dissolved.
Comparative example 2
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows:
in a glove box filled with argon, 40g of lithium bis (trifluoromethanesulfonyl) imide were added to 60g of a non-aqueous organic solvent (trimethyl phosphate and dimethyl carbonate in a volume ratio of 3: 7) and stirred until it was completely dissolved.
Comparative example 3
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows:
in a glove box filled with argon, 3g of lithium bis (oxalato) borate, 3g of vinylene carbonate, 0.1g of LiClO4And 20g of lithium bis (fluorosulfonyl) imide were added to 73.9 nonaqueous organic solvent (trimethyl phosphate), and stirred until it was completely dissolved.
Comparative example 4
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows:
in a glove box filled with argon, 3g of lithium bis (oxalato) borate, 3g of vinylene carbonate, 0.1g of LiClO4And 20g of lithium bis (fluorosulfonyl) imide were added to 73.9g of a nonaqueous organic solvent (trimethyl phosphate and propylene carbonate in a volume ratio of 3: 7), and stirred until it was completely dissolved.
Comparative example 5
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows:
in a glove box filled with argon, 3g of lithium bis (oxalato) borate, 3g of vinylene carbonate, 0.1g of LiClO4And 20g of lithium bis (fluorosulfonyl) imide were added to 73.9g of a nonaqueous organic solvent (trimethyl phosphate, propylene carbonate in a volume ratio of 3: 2), and stirred until it was completely dissolved.
Comparative example 6
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 40g of lithium bis (trifluoromethanesulfonyl) imide was added to 60g of a nonaqueous organic solvent (trimethyl phosphate and propylene carbonate in a volume ratio of 7: 3), and stirred until completely dissolved, to prepare a nonaqueous electrolytic solution for a lithium ion battery.
Comparative example 7
The preparation method is basically the same as that of the example 1, except that the preparation steps of the nonaqueous electrolyte for the lithium ion battery are as follows: 40g of lithium bis (trifluoromethanesulfonyl) imide was added to 60g of a nonaqueous organic solvent (trimethyl phosphate, ethyl methyl carbonate, and 2,2, 2-trifluoroethyl carbonate in a volume ratio of 7:2: 1), and stirred until completely dissolved, to prepare a nonaqueous electrolytic solution for a lithium ion battery.
The compositions (the total of the weight percentages of the components is 100%) of the electrolytes prepared in examples 1 to 9 and comparative examples 1 to 7 are shown in the following table 1:
TABLE 1
Test example
1. Test for non-flammability
The test method comprises the following steps: 5mL of each of the electrolytes prepared in examples 1 to 9 and comparative examples 1 to 7 was used as a test sample and placed in a beaker, and a test for ignition was performed on each sample using a lighter.
2. Cycle performance test
The lithium ion button cells prepared in examples 1 to 12 and comparative examples 1 to 5 were used as samples and allowed to stand at room temperature (25 ℃) for 24 hours. The battery samples were subjected to a cycling test using a blue cell charge and discharge tester (purchased from blue electronic, inc., wuhan).
The test conditions were: cycling at 0.1C for 1 week, then at 0.2C for 3 weeks, and then at 0.5C for 200 weeks at room temperature (25 deg.C), wherein the charging and discharging voltage of the battery is controlled to be 2.5V-3.8V.
The results of the flame retardant performance test and the cycle performance test of each of the above samples are shown in table 2 below:
TABLE 2
As can be seen from Table 2, the electrolytes of comparative examples 2,4 and 5 cannot achieve flame retardancy by comparing examples 1 to 9 with comparative examples 1 to 7; the batteries prepared by the electrolytes of comparative example 1 and comparative examples 6 to 7 are incombustible, but fail after 1 week of circulation; the battery prepared by the electrolyte of the comparative example 3 is non-combustible and does not fail after 200 cycles, but the battery has low 0.5C specific discharge capacity and the capacity retention rate after 200 cycles is only 20.1%, while the batteries prepared by the electrolytes of the examples 1 to 12 are non-combustible and still effective after 200 cycles, the 0.5C specific discharge capacity is more than 100mAh/g, and the capacity retention rate of the battery is still more than 66.17% after 200 cycles.
The comparison shows that the second ester solvent and the phosphate ester solvent of a specific type are matched with each other in a specific proportion, and then a specific amount of the additive for inhibiting the stripping of the negative electrode and the sulfimide salt are matched, so that the constructed electrolyte system is used for the battery, and the battery has good incombustibility, cycle performance and rate capability.
In addition, as can be seen from the comparison between examples 1 to 9, the cycle performance and rate capability of the batteries prepared by the electrolytes in examples 1 to 2 are better than those in examples 3 and 4, which shows that when the organic solvent is a mixture of a phosphate ester solvent and a second ester solvent, the content of the second ester solvent is more preferably greater than 10%, and when the organic solvent is a mixture of a phosphate ester solvent, a second ester solvent and a fluorinated solvent, the content of the phosphate ester solvent is more preferably equal to or less than 80%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A nonaqueous electrolyte for a lithium ion battery, comprising an organic solvent, a lithium sulfonimide salt and an additive for suppressing negative electrode exfoliation, wherein the organic solvent comprises a mixture of a phosphate-based solvent and a second ester-based solvent, and the second ester-based solvent is a carbonate-based solvent and/or a fatty ester-based solvent having a structure represented by the following formula (I):
in the formula (I), R1Selected from alkyl or alkoxy groups having 1 to 4 carbon atoms, R2Selected from alkyl groups having 1 to 4 carbon atoms, or, R1And R2Bonding with each other and forming a ring with 3-6 carbon atoms together with adjacent carbonyl carbon atoms and oxygen atoms, wherein the atoms bonded with the carbonyl carbon atoms in the ring are all oxygen;
in the non-aqueous electrolyte, the content of the lithium sulfonimide salt is 20-45 wt%, the content of the additive is 0.3-20 wt%, and the content of the organic solvent is 50-75 wt%, wherein the phosphate solvent accounts for 50-90% of the volume of the organic solvent, and the second ester solvent accounts for 10-30% of the volume of the organic solvent.
2. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the carbonate-based solvent is one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, and ethyl methyl carbonate;
the fatty ester solvent is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate.
3. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the phosphate-based solvent is one or more selected from the group consisting of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trioctyl phosphate, dimethyl phosphate, dibutyl phosphate, triallyl phosphate, trimethyl phosphite, triethyl phosphite, dibutyl phosphite, triisopropyl phosphite, dimethyl-vinyl phosphate, diethyl vinyl phosphate, and dimethyl vinyl phosphate.
4. The nonaqueous electrolyte for a lithium ion battery according to claim 1, wherein the organic solvent is a mixture of a phosphate-based solvent and a second ester-based solvent, and the volume ratio of the phosphate-based solvent to the second ester-based solvent is (7-9): (1-3).
5. The nonaqueous electrolyte for a lithium ion battery according to claim 1, wherein the organic solvent further comprises a fluorinated solvent selected from fluoroethers and/or fluorinated carbonates having a degree of substitution with fluorine of 50% or more and 2 to 6 carbon atoms.
6. The nonaqueous electrolyte solution for a lithium ion battery according to claim 5, wherein the fluorinated solvent is one or more selected from the group consisting of 1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether, 1- (2,2, 2-trifluoroethoxy) -1,1,2, 2-tetrafluoroethane, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 3,3, 3-trifluoropropene carbonate and bis (2,2, 2-trifluoroethyl) carbonate.
7. The nonaqueous electrolyte for a lithium ion battery according to claim 5 or 6, wherein the organic solvent is a mixture of a phosphate-based solvent, a second ester-based solvent and a fluorinated solvent, and the volume ratio of the phosphate-based solvent, the second ester-based solvent and the fluorinated solvent is (5 to 8.95): (1-3): (0.05-3).
8. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the additive comprises a phosphorus-containing additive, a negative electrode reducing agent, and an aluminum current collector protecting agent, or the additive comprises a boron-containing additive, a negative electrode reducing agent, and an aluminum current collector protecting agent,
in the non-aqueous electrolyte, the content of the phosphorus-containing additive or the boron-containing additive is 0.1 to 5 wt%, the content of the negative electrode reducing agent is 0.1 to 3 wt%, and the content of the aluminum current collector protective agent is 0.1 to 5 wt%.
9. The nonaqueous electrolyte for a lithium ion battery according to claim 8, wherein the phosphorus-containing additive is one or more selected from lithium difluorophosphate, lithium difluorooxalate phosphate, lithium tetrafluorooxalate phosphate, dilithium acetylphosphate, and dilithium carbamoylphosphate; the boron-containing additive is selected from one or more of lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate and lithium trifluoro (trifluoromethyl) borate; the negative reducing agent is selected from one or more of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, ethylene vinyl carbonate, ethylene sulfate, ethylene sulfite, ethylene sulfate, ethylene carbonate, propylene sulfate, 1, 4-butane sultone, 1, 3-propane sultone and tris (trimethylsilyl) borate; the aluminum current collector protective agent is selected from LiClO4、LiAsF6、LiPF6、LiBF4One or more of LiBOB, LiDFOB and nitrile compounds.
10. The nonaqueous electrolyte solution for a lithium ion battery according to claim 1, wherein the lithium sulfonimide salt is one or more selected from the group consisting of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium 1,1,2,2,3, 3-hexafluoropropane-1, 3-disulfonyl imide, lithium bis (nonafluorobutylsulfonyl) imide, and lithium bis (1,1,1,3,3, 3-hexafluoroisopropoxysulfonyl) imide.
11. A lithium ion battery comprising a positive electrode, a negative electrode and the nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 10.
12. The lithium ion battery of claim 11, wherein the positive electrode comprises an aluminum current collector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110350949.4A CN113161612B (en) | 2021-03-31 | 2021-03-31 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110350949.4A CN113161612B (en) | 2021-03-31 | 2021-03-31 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113161612A true CN113161612A (en) | 2021-07-23 |
| CN113161612B CN113161612B (en) | 2022-07-22 |
Family
ID=76885866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110350949.4A Active CN113161612B (en) | 2021-03-31 | 2021-03-31 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113161612B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113764736A (en) * | 2021-09-09 | 2021-12-07 | 深圳市研一新材料有限责任公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
| WO2023221120A1 (en) * | 2022-05-20 | 2023-11-23 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte, secondary battery comprising same, battery module, battery pack, and electric device |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5580684A (en) * | 1994-07-07 | 1996-12-03 | Mitsui Petrochemical Industries, Ltd. | Non-aqueous electrolytic solutions and non-aqueous electrolyte cells comprising the same |
| US20020009644A1 (en) * | 2000-03-01 | 2002-01-24 | Seiji Yoshimura | Rechargeable lithium battery |
| CN1411619A (en) * | 2001-01-04 | 2003-04-16 | 三菱化学株式会社 | Nonaqueous electrolytic liquid and lithium secondary battery employing same |
| KR20060014280A (en) * | 2004-08-10 | 2006-02-15 | 제일모직주식회사 | Non-aqueous electrolyte for secondary batteries and secondary batteries containing the same |
| CN104078699A (en) * | 2013-03-26 | 2014-10-01 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN105703007A (en) * | 2016-03-30 | 2016-06-22 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte for high-voltage rapid-charging type lithium ion battery |
| CN105895953A (en) * | 2016-04-25 | 2016-08-24 | 何凤英 | Flame-retardant electrolyte for lithium ion battery and preparation method of flame-retardant electrolyte |
| CN109818059A (en) * | 2019-01-29 | 2019-05-28 | 厦门首能科技有限公司 | A kind of electrolyte of lithium ion secondary battery |
| CN112110953A (en) * | 2020-04-29 | 2020-12-22 | 湖州师范学院 | Phosphate compound, synthetic method and non-aqueous electrolyte thereof |
-
2021
- 2021-03-31 CN CN202110350949.4A patent/CN113161612B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5580684A (en) * | 1994-07-07 | 1996-12-03 | Mitsui Petrochemical Industries, Ltd. | Non-aqueous electrolytic solutions and non-aqueous electrolyte cells comprising the same |
| US20020009644A1 (en) * | 2000-03-01 | 2002-01-24 | Seiji Yoshimura | Rechargeable lithium battery |
| CN1411619A (en) * | 2001-01-04 | 2003-04-16 | 三菱化学株式会社 | Nonaqueous electrolytic liquid and lithium secondary battery employing same |
| KR20060014280A (en) * | 2004-08-10 | 2006-02-15 | 제일모직주식회사 | Non-aqueous electrolyte for secondary batteries and secondary batteries containing the same |
| CN104078699A (en) * | 2013-03-26 | 2014-10-01 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| CN105703007A (en) * | 2016-03-30 | 2016-06-22 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte for high-voltage rapid-charging type lithium ion battery |
| CN105895953A (en) * | 2016-04-25 | 2016-08-24 | 何凤英 | Flame-retardant electrolyte for lithium ion battery and preparation method of flame-retardant electrolyte |
| CN109818059A (en) * | 2019-01-29 | 2019-05-28 | 厦门首能科技有限公司 | A kind of electrolyte of lithium ion secondary battery |
| CN112110953A (en) * | 2020-04-29 | 2020-12-22 | 湖州师范学院 | Phosphate compound, synthetic method and non-aqueous electrolyte thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113764736A (en) * | 2021-09-09 | 2021-12-07 | 深圳市研一新材料有限责任公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
| CN113764736B (en) * | 2021-09-09 | 2024-02-06 | 深圳市研一新材料有限责任公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
| WO2023221120A1 (en) * | 2022-05-20 | 2023-11-23 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte, secondary battery comprising same, battery module, battery pack, and electric device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113161612B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109873205B (en) | Electrolyte suitable for silicon-carbon cathode and lithium ion battery containing electrolyte | |
| US10056649B2 (en) | Non-aqueous electrolytic solutions and electrochemical cells comprising the same | |
| CN102742064B (en) | Non-aqueous electrolytic solution, and the lithium rechargeable battery with described non-aqueous electrolytic solution | |
| WO2020151647A1 (en) | Electrolyte solution and electrochemical device using the same | |
| CN109888383B (en) | Electrolyte and lithium ion battery | |
| CN111430793B (en) | Electrolyte solution, and electrochemical device and electronic device using same | |
| CA2821958A1 (en) | Battery electrolyte solution containing certain ester-based solvents, and batteries containing such an electrolyte solution | |
| CN111628219A (en) | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device | |
| CN112400249A (en) | Electrolyte and electrochemical device | |
| CN113161612B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same | |
| CN110970662B (en) | Non-aqueous electrolyte and lithium ion battery | |
| US8709665B2 (en) | Nonaqueous secondary battery with nitrile group-containing compound | |
| JP7278658B2 (en) | Electrolyte for lithium secondary battery and lithium secondary battery containing the same | |
| CN113161610B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same | |
| CN109994777A (en) | Electrolyte solution and secondary battery | |
| JP2015069705A (en) | Nonaqueous electrolytic solution for secondary batteries, and lithium ion secondary battery | |
| US20210408602A1 (en) | Electrolyte and electrochemical device | |
| CN110970660A (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN110970663A (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN113161611B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same | |
| CN110970652A (en) | Non-aqueous electrolyte and lithium ion battery | |
| JP7460260B2 (en) | Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same | |
| CA3233090A1 (en) | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| EP4343914A1 (en) | Lithium secondary battery | |
| CN110970661A (en) | Non-aqueous electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221108 Address after: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000 Patentee after: Material Laboratory of Songshan Lake Patentee after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES Address before: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000 Patentee before: Material Laboratory of Songshan Lake |
|
| TR01 | Transfer of patent right |