CN111244541B - Electrolyte and electrochemical device using the same - Google Patents

Electrolyte and electrochemical device using the same Download PDF

Info

Publication number
CN111244541B
CN111244541B CN202010064859.4A CN202010064859A CN111244541B CN 111244541 B CN111244541 B CN 111244541B CN 202010064859 A CN202010064859 A CN 202010064859A CN 111244541 B CN111244541 B CN 111244541B
Authority
CN
China
Prior art keywords
electrolyte
compound
lithium
positive electrode
active material
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.)
Active
Application number
CN202010064859.4A
Other languages
Chinese (zh)
Other versions
CN111244541A (en
Inventor
栗文强
刘建
管明明
郑建明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningde Amperex Technology Ltd
Original Assignee
Ningde Amperex Technology Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ningde Amperex Technology Ltd filed Critical Ningde Amperex Technology Ltd
Priority to CN202010064859.4A priority Critical patent/CN111244541B/en
Publication of CN111244541A publication Critical patent/CN111244541A/en
Application granted granted Critical
Publication of CN111244541B publication Critical patent/CN111244541B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • H01M10/0567—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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present application relates to an electrolyte and an electrochemical device using the same. The electrolyte of the present application comprises a compound of formula I:

Description

Electrolyte and electrochemical device using the same
Technical Field
The present application relates to the technical field of electrochemical devices, and more particularly, to an electrolyte and an electrochemical device using the same.
Background
High energy density is a relatively large trend in the development of lithium ion batteries. With the rapid development of 5G in recent years and the continuous development of light weight and miniaturization of intelligent devices, the volume of batteries is smaller and smaller, and the energy required to be provided by the batteries is higher and higher. High voltages provide a relatively efficient solution and approach to energy density improvement, but high voltages are accompanied by serious safety issues. Solving the safety problem becomes a necessary way for the development of the lithium ion battery to high voltage.
The present application provides an electrolyte and an electrochemical device using the same to solve the above problems.
Disclosure of Invention
Embodiments of the present application provide an electrolyte and an electrochemical device using the same in an attempt to solve at least one problem existing in the related art to at least some extent. The embodiment of the application also provides an electrochemical device and an electronic device using the electrolyte.
In one aspect of the present application, there is provided an electrolyte comprising a compound of formula I and a carboxylate compound:
wherein R is 11 、R 12 、R 13 、R 14 Each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 1-20 Alkoxy, substituted or unsubstituted C 3-20 Heterocyclic group, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 6-20 Heteroaryl or-R 0 -an O-R group, a substituted or unsubstituted sultone, wherein a heteroatom in the heterocyclic group is selected from at least one of O, S, N or P; or R is 11 And R is 12 Together with the carbon atom to which it is attached, form a 5-10 membered cyclic structure, wherein the cyclic structure optionally contains a heteroatom selected from at least one of O, S, N or P;
Wherein R is 0 Selected from C 1-6 Alkylene, R is selected from sulfonyl, methylsulfonyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 6-20 Heteroaryl;
wherein R is 11 、R 12 、R 13 、R 14 When R is independently substituted, the substituent is selected from halogen, cyano, sulfonyl, methylsulfonyl, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl, C 6-20 Heteroaryl, or any combination thereof.
In some embodiments, the R 11 、R 12 、R 13 、R 14 Each independently selected from the following groups:
H、 or (b)
R 11 And R is 12 Together with the carbon atom to which it is attached to form
In some embodiments, the weight percent of the compound of formula I is a wt%, a is 0.001 to 5, based on the total weight of the electrolyte.
In some embodiments, the compound of formula I comprises at least one of the following compounds:
in some embodiments, the carboxylate compound comprises a compound of formula II:
wherein R is 21 、R 22 Each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 1-20 Alkoxy, substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 6-20 Heteroaryl;
wherein R is 21 、R 22 Each independently substituted, the substituents are selected from halogen, cyano, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl or any combination thereof;
in some embodiments, the weight percent of the carboxylate compound is b wt%, b is 0.05 to 75, based on the total weight of the electrolyte.
In some embodiments, the carboxylate compound comprises at least one of the following compounds:
in some embodiments, the electrolyte further comprises a compound of formula III:
wherein M is selected from one of C, si;
R 31 、R 32 、R 33 each independently selected from substituted or unsubstituted C 1 -C 20 Alkylene, substituted or unsubstituted C 2 -C 20 Alkenylene, -R 35 -S-R 36 -or-R 37 -O-R 38 -，R 35 、R 36 、R 37 And R is 38 Each independently is a single bond, substituted or unsubstituted C 1 -C 20 Alkylene or substituted or unsubstituted C 2 -C 20 Alkenylene;
R 34 selected from H, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl groups;
wherein R is 31 、R 32 、R 33 、R 34 、R 35 、R 36 、R 37 And R is 38 Each independently substituted, the substituents are selected from halogen, cyano, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl or any combination thereof;
in some embodiments, the weight percent of the compound of formula III is 0.01wt% to 5wt%, based on the total weight of the electrolyte.
In some embodiments, the compound of formula III comprises at least one of the following compounds:
in some embodiments, the electrolyte further comprises a lithium salt additive comprising at least one of the following lithium salts: liPO (LiPO) 2 F 2 Lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium tetrafluoro-phosphate oxalate, lithium difluorooxalato borate, or lithium hexafluorocesium acid;
in some embodiments, the weight percent of the lithium salt additive is 0.001wt% to 5wt%, based on the total weight of the electrolyte.
In another aspect of the present application, there is provided an electrochemical device including a positive electrode active material layer including a positive electrode active material; and an electrolyte according to embodiments of the present application.
In some embodiments, the electrolyte of the electrochemical device further includes copper ions, the copper ions being contained in an amount of 0.01ppm to 50ppm based on the total weight of the electrolyte.
In some embodiments, the positive electrode active material contains Ti element in an amount of t×10 based on the total weight of the positive electrode active material layer 2 ppm, t is from 2 to 10, and (a+b)/t.ltoreq.35.
In another aspect of the present application, the present application provides an electronic device comprising an electrochemical device according to an embodiment of the present application.
Lithium ion batteries prepared from the electrolytes of the present application have reduced storage impedance and improved storage gassing and overcharge and hot-box performance.
Additional aspects and advantages of embodiments of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of embodiments of the application.
Detailed Description
Embodiments of the present application will be described in detail below. The examples of the present application should not be construed as limiting the present application.
In the detailed description and claims, a list of items connected by the terms "one of," "one of," or other similar terms may mean any of the listed items. For example, if items a and B are listed, the phrase "one of a and B" means either only a or only B. In another example, if items A, B and C are listed, one of the phrases "A, B and C" means only a; only B; or only C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
In the detailed description and claims, a list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
As used herein, the term "alkyl" is intended to be a straight chain saturated hydrocarbon structure having from 1 to 20 carbon atoms. "alkyl" is also intended to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms. For example, the alkyl group may be an alkyl group of 1 to 20 carbon atoms, an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 5 carbon atoms, an alkyl group of 5 to 20 carbon atoms, an alkyl group of 5 to 15 carbon atoms, or an alkyl group of 5 to 10 carbon atoms. When alkyl groups having a specific carbon number are specified, all geometric isomers having that carbon number are contemplated; thus, for example, reference to "butyl" is intended to include n-butyl, sec-butyl, isobutyl, tert-butyl and cyclobutyl; "propyl" includes n-propyl, isopropyl and cyclopropyl. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, and the like. In addition, the alkyl group may be optionally substituted.
As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Cycloalkyl groups may be cycloalkyl groups of 3 to 20 carbon atoms, cycloalkyl groups of 6 to 20 carbon atoms, cycloalkyl groups of 3 to 12 carbon atoms, cycloalkyl groups of 3 to 6 carbon atoms. For example, cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. In addition, cycloalkyl groups may be optionally substituted.
As used herein, the term "alkoxy" refers to an L-O-group, wherein L is an alkyl group. For example, the alkoxy group may be an alkoxy group of 1 to 20 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxy group of 5 to 20 carbon atoms, an alkoxy group of 5 to 15 carbon atoms, or an alkoxy group of 5 to 10 carbon atoms. In addition, the alkoxy groups may be optionally substituted.
As used herein, the term "alkenyl" refers to a monovalent unsaturated hydrocarbon group that may be straight or branched and has at least one, and typically 1, 2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group generally contains 2 to 20 carbon atoms, for example, can be an alkenyl group of 2 to 20 carbon atoms, an alkenyl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyl group of 2 to 6 carbon atoms. Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. In addition, alkenyl groups may be optionally substituted.
As used herein, the term "alkylene" means a straight or branched divalent saturated hydrocarbon group. For example, the alkylene group may be an alkylene group of 1 to 20 carbon atoms, an alkylene group of 1 to 15 carbon atoms, an alkylene group of 1 to 10 carbon atoms, an alkylene group of 1 to 5 carbon atoms, an alkylene group of 5 to 20 carbon atoms, an alkylene group of 5 to 15 carbon atoms or an alkylene group of 5 to 10 carbon atoms. Representative alkylene groups include, for example, methylene, ethane-1, 2-diyl ("ethylene"), propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, and the like. In addition, the alkylene group may be optionally substituted.
As used herein, the term "alkenylene" encompasses both straight and branched chain alkenylenes. When an alkenylene group having a specific carbon number is specified, all geometric isomers having that carbon number are contemplated. For example, the alkenylene group may be an alkenylene group of 2 to 20 carbon atoms, an alkenylene group of 2 to 15 carbon atoms, an alkenylene group of 2 to 10 carbon atoms, an alkenylene group of 2 to 5 carbon atoms, an alkenylene group of 5 to 20 carbon atoms, an alkenylene group of 5 to 15 carbon atoms, or an alkenylene group of 5 to 10 carbon atoms. Representative alkenylenes include, for example, ethenylenes, propenylenes, butenylene, and the like. In addition, alkenylene groups may be optionally substituted.
As used herein, the term "heterocyclic group" encompasses both aromatic and non-aromatic cyclic groups. Heteroaromatic cyclic groups also mean heteroaryl groups. In some embodiments, the heteroaromatic ring groups and the heteroaromatic ring groups are C including at least one heteroatom 3 -C 20 Heterocyclyl, C 3 -C 150 Heterocyclyl, C 3 -C 10 Heterocyclyl, C 5 -C 20 Heterocyclyl, C 5 -C 10 Heterocyclyl, C 3 -C 6 A heterocyclic group. Such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. In addition, the heterocyclic group may be optionally substituted.
As used herein, the term "aryl" encompasses both monocyclic and polycyclic systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is aromatic, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. For example, aryl may be C 6 -C 50 Aryl, C 6 -C 40 Aryl, C 6 -C 30 Aryl, C 6 -C 20 Aryl or C 6 -C 10 Aryl groups. Representative aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl, and naphthalen-1-yl, naphthalen-2-yl, and the like. In addition, aryl groups may be optionally substituted.
As used herein, the term "heteroaryl" encompasses monocyclic heteroaromatic groups that may include one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyrimidine, and the like. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl and the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl. The heteroatom in the heteroaryl group may be O, S, N, se or the like, for example. For example, heteroaryl may be C 3 -C 50 Heteroaryl, C 3 -C 40 Heteroaryl, C 3 -C 30 Heteroaryl, C 3 -C 20 Heteroaryl or C 3 -C 10 Heteroaryl groups. Additionally, heteroaryl groups may be optionally substituted.
As used herein, the term "dinitrile compound" refers to a compound containing two-CN functional groups.
As used herein, the term "heteroatom" encompasses O, S, P, N, B or an isostere thereof.
As used herein, the term "halogen" encompasses F, cl, br, I.
When the above substituents are substituted, their substituents may each be independently selected from the group consisting of: halogen, alkyl, alkenyl, aryl.
As used herein, the term "substituted" or "substituted" means that it may be substituted with 1 or more (e.g., 2, 3) substituents.
As used herein, the content of each component is based on the total weight of the electrolyte.
1. Electrolyte solution
In some embodiments, the present application provides an electrolyte comprising a compound of formula I and a carboxylate compound:
wherein R is 11 、R 12 、R 13 、R 14 Each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 1-20 Alkoxy, substituted or unsubstituted C 3-20 Heterocyclic group, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 6-20 Heteroaryl or-R 0 -an O-R group, a substituted or unsubstituted sultone, wherein a heteroatom in the heterocyclic group is selected from at least one of O, S, N or P; or R is 11 And R is 12 Together with the carbon atom to which it is attached, form a 5-10 membered cyclic structure, wherein the cyclic structure optionally contains a heteroatom selected from at least one of O, S, N or P; the cyclic structure may be a saturated or unsaturated structure.
Wherein R is 0 Selected from C 1-6 Alkylene, R is selected from sulfonyl, methylsulfonyl, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 6-20 Heteroaryl;
wherein R is 11 、R 12 、R 13 、R 14 When R is independently substituted, the substituent is selected from halogen, cyano, sulfonyl, methylsulfonyl, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl, C 6-20 Heteroaryl, or any combination thereof.
In some embodiments, the R 11 、R 12 、R 13 、R 14 Each independently selected from the following groups:
H、 or (b)
R 11 And R is 12 Together with the carbon atom to which it is attached to form
In some embodiments, the weight percent of the compound of formula I is a wt%, a is 0.001 to 5, based on the total weight of the electrolyte. In some embodiments, the weight percent of the compound of formula I is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, or a range of any two of these values, based on the total weight of the electrolyte. The content of the compound of the formula I in the range can form a better protective film, and can more effectively prevent side reactions of electrolyte and a positive electrode or a negative electrode.
In some embodiments, the compound of formula I comprises or is selected from at least one of the following compounds:
the combination of the compound of the formula I and the fluorinated carboxylic ester can fully exert the stability of the organic protective film and the oxidation resistance of the electrolyte, and can effectively improve the hot box and the overcharge performance. Although the detailed mechanism of action to obtain this effect is not known, the following can be considered: the compound of the formula I and the fluoro-carboxylic ester act together, so that the oxidation resistance of an electrolyte system is improved, and the additive is more beneficial to film formation at the positive electrode and the negative electrode, so that the active material is effectively protected; as the temperature increases, the protection of the active material by the organic protective film gradually decreases. The compound of the formula I and the fluoro-carboxylic ester act together to effectively reduce chemical heat generation and improve the safety performance of the electrochemical device.
In some embodiments, the carboxylate compound comprises or is selected from the group consisting of compounds of formula II:
wherein R is 21 、R 22 Each independently selected from H, halogen, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 1-20 Alkoxy, substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 6-20 Heteroaryl;
wherein R is 21 、R 22 Each independently substituted, the substituents are selected from halogen, cyano, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl or any combination thereof;
in some embodiments, the weight percent of the carboxylate compound is b wt%, b is 0.05 to 75, based on the total weight of the electrolyte. In some embodiments, the weight percent of the carboxylate compound is 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, or a range of any two of these values, based on the total weight of the electrolyte. When the carboxylate content is within this range, the electrochemical device has better overcharge performance and hot-box performance.
In some embodiments, the carboxylate compound comprises or is selected from at least one of the following:
in some embodiments, the electrolyte further comprises a compound of formula III:
wherein M is selected from one of C, si;
R 31 、R 32 、R 33 each independently selected from substituted or unsubstituted C 1 -C 20 Alkylene, substituted or unsubstituted C 2 -C 20 Alkenylene, -R 35 -S-R 36 -or-R 37 -O-R 38 -，R 35 、R 36 、R 37 And R is 38 Each independently is a single bond, substituted or unsubstituted C 1 -C 20 Alkylene or substituted or unsubstituted C 2 -C 20 Alkenylene;
R 34 selected from H, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl groups;
wherein R is 31 、R 32 、R 33 、R 34 、R 35 、R 36 、R 37 And R is 38 Each independently substituted, the substituents are selected from halogen, cyano, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 1-20 Alkoxy, C 2-20 Alkenyl, C 6-20 Aryl groups, or any combination thereof.
The combination of the compound of formula I, the carboxylate compound and the compound of formula III may further improve the overcharge performance of the electrochemical device while improving the high temperature storage expansion problem of the electrochemical device. Although the detailed mechanism of action to obtain this effect is not known, the following can be considered: the combined action of the compound of the formula I, the carboxylate compound and the compound of the formula III can further reduce the risk of oxidizing the electrolyte, improve the protection of the positive electrode, and reduce the direct contact between the interface of the positive electrode active material and the electrolyte, so that the flatulence caused by the contact between the electrolyte and the positive electrode active material during high-temperature storage can be reduced.
In some embodiments, the weight percent of the compound of formula III is 0.01wt% to 5wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the compound of formula III is 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, or a range of any two of these values, based on the total weight of the electrolyte. The weight percent of the compound of formula III in this range results in better overcharge performance and better high temperature storage performance.
In some embodiments, the compound of formula III comprises or is selected from at least one of the following compounds:
in some embodiments, the electrolyte further comprises a lithium salt additive comprising at least one of the following lithium salts: liPO (LiPO) 2 F 2 Lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium tetrafluoro-phosphate oxalate, lithium difluorooxalato borate, or lithium hexafluorocesium acid.
In some embodiments, the weight percent of the lithium salt additive is 0.001wt% to 5wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the lithium salt additive is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, or a range of any two of these values, based on the total weight of the electrolyte.
In some embodiments, the electrolyte further comprises a dinitrile compound. The dinitrile compound can compensate the film forming defect of the compound of the formula III due to smaller steric hindrance, so that the interface protection of the positive electrode active material is enhanced.
In some embodiments, the dinitrile compounds include, but are not limited to: succinonitrile, glutaronitrile, adiponitrile, 1, 5-dicyanopentane, 1, 6-dicyanohexane, 1, 7-dicyanoheptane, 1, 8-dicyanooctane, 1, 9-dicyanononane, 1, 10-dicyanodecane, 1, 12-dicyanododecane, tetramethylsuccinonitrile, 2-methylglutaronitrile, 2, 4-dimethylglutaronitrile, 2, 4-tetramethylglutaronitrile, 1, 4-dicyanopentane, 2, 5-dimethyl-2, 5-hexanedicarbonitrile, 2, 6-dicyanoheptane, 2, 7-dicyanooctane, 2, 8-dicyanononane, 1, 6-dicyanodecane, 1, 2-dicyanobenzene, 1, 3-dicyanobenzene 1, 4-dicyanobenzene, 3, 5-dioxa-pimelic acid dinitrile, 1, 4-bis (cyanoethoxy) butane, ethylene glycol bis (2-cyanoethyl) ether, diethylene glycol bis (2-cyanoethyl) ether, triethylene glycol bis (2-cyanoethyl) ether, tetraethylene glycol bis (2-cyanoethyl) ether, 3,6,9,12,15,18-hexaeicosanoic acid dinitrile, 1, 3-bis (2-cyanoethoxy) propane, 1, 4-bis (2-cyanoethoxy) butane, 1, 5-bis (2-cyanoethoxy) pentane and ethylene glycol bis (4-cyanobutyl) ether, 1, 4-dicyano-2-butene, 1, 4-dicyano-2-methyl-2-butene, 1, 4-dicyano-2-ethyl-2-butene, 1, 4-dicyano-2, 3-dimethyl-2-butene, 1, 4-dicyano-2, 3-diethyl-2-butene, 1, 6-dicyano-3-hexene, 1, 6-dicyano-2-methyl-5-methyl-3-hexene.
In some embodiments, the weight percent of the dinitrile compound is 0.1wt% to 15wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not less than 0.1wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not less than 0.5wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not less than 2wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not less than 4wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not greater than 15wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not greater than 10wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the dinitrile compound is not greater than 8wt% based on the total weight of the electrolyte.
In some embodiments, the electrolyte further comprises a cyclic ether. The cyclic ether can form a film at the positive and negative electrodes at the same time, so that the reaction between the electrolyte and the active material is reduced.
In some embodiments, the cyclic ether includes, but is not limited to: tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, dimethoxypropane.
In some embodiments, the weight percent of the cyclic ether is 0.1wt% to 10wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the cyclic ether is not less than 0.1wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the cyclic ether is not less than 0.5wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the cyclic ether is not greater than 2wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the cyclic ether is no greater than 5wt%, based on the total weight of the electrolyte.
In some embodiments, the electrolyte further comprises a chain ether. In some embodiments, the chain ethers include, but are not limited to: dimethoxymethane, 1-dimethoxyethane, 1, 2-dimethoxyethane, diethoxymethane, 1-diethoxyethane, 1, 2-diethoxyethane, ethoxymethoxymethane, 1-ethoxymethoxyethane, 1, 2-ethoxymethoxyethane.
In some embodiments, the weight percent of the chain ether is 0.1wt% to 10wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the chain ether is not less than 0.5wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the chain ether is not less than 2wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the chain ether is not less than 3wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the chain ether is no greater than 10wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the chain ether is no greater than 5wt%, based on the total weight of the electrolyte.
In some embodiments, the electrolyte further comprises a phosphorus-containing organic solvent. In some embodiments, the phosphorus-containing organic solvent includes, but is not limited to: trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris (2, 2-trifluoroethyl) phosphate, tris (2, 3-pentafluoropropyl) phosphate.
In some embodiments, the weight percent of the phosphorus-containing organic solvent is from 0.1wt% to 10wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the phosphorus-containing organic solvent is not less than 0.1wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the phosphorus-containing organic solvent is not less than 0.5wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the phosphorus-containing organic solvent is no greater than 2wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the phosphorus-containing organic solvent is no greater than 3wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the phosphorus-containing organic solvent is no greater than 5wt%, based on the total weight of the electrolyte.
In some embodiments, the electrolyte further comprises an aromatic fluorine-containing solvent. The aromatic fluorine-containing solvent can rapidly form a film to protect the active material, and the fluorine-containing substance can promote the infiltration performance of the electrolyte on the active material. In some embodiments, the aromatic fluorine-containing solvent includes, but is not limited to: fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, trifluoromethyl benzene.
In some embodiments, the weight percent of the aromatic fluorine-containing solvent is about 0.1wt% to 10wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the aromatic fluorine-containing solvent is not less than 0.5wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the aromatic fluorine-containing solvent is not less than 2wt% based on the total weight of the electrolyte. In some embodiments, the weight percent of the aromatic fluorine-containing solvent is not greater than 4wt%, based on the total weight of the electrolyte. In some embodiments, the weight percent of the aromatic fluorine-containing solvent is not greater than 8wt%, based on the total weight of the electrolyte.
2. Electrolyte composition
The electrolyte used in the electrolyte of the embodiments of the present application may be any electrolyte known in the art, including, but not limited to: inorganic lithium salts, e.g. LiClO 4 、LiAsF 6 、LiPF 6 、LiBF 4 、LiSbF 6 、LiSO 3 F、LiN(FSO 2 ) 2 Etc.; fluorine-containing organolithium salts, e.g. LiCF 3 SO 3 、LiN(FSO 2 )(CF 3 SO 2 )、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 Lithium, cyclic 1, 3-hexafluoropropane disulfonimide, lithium, cyclic 1, 2-tetrafluoroethane disulfonimide, liN (CF) 3 SO 2 )(C 4 F 9 SO 2 )、LiC(CF 3 SO 2 ) 3 、LiPF 4 (CF 3 ) 2 、LiPF 4 (C 2 F 5 ) 2 、LiPF 4 (CF 3 SO 2 ) 2 、LiPF 4 (C 2 F 5 SO 2 ) 2 、LiBF 2 (CF 3 ) 2 、LiBF 2 (C 2 F 5 ) 2 、LiBF 2 (CF 3 SO 2 ) 2 、LiBF 2 (C 2 F 5 SO 2 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Examples of the dicarboxylic acid-containing complex lithium salt include lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tris (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate, and the like. In addition, one kind of the above electrolytes may be used alone, or two or more kinds may be used simultaneously The above. For example, in some embodiments, the electrolyte includes LiPF 6 And LiBF 4 Is a combination of (a) and (b). In some embodiments, the electrolyte comprises LiPF 6 Or LiBF 4 Equal inorganic lithium salt and LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 And combinations of fluorine-containing organolithium salts. In some embodiments, the concentration of the electrolyte is in the range of 0.8-3mol/L, such as in the range of 0.8-2.5mol/L, in the range of 0.8-2mol/L, in the range of 1-2mol/L, 0.5-1.5mol/L, 0.8-1.3mol/L, 0.5-1.2mol/L, and further such as 1mol/L, 1.15mol/L, 1.2mol/L, 1.5mol/L, 2mol/L, or 2.5mol/L.
3. Electrochemical device
The electrochemical device of the present application includes any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors. In particular, the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery. In some embodiments, the electrochemical device of the present application is an electrochemical device including a positive electrode having a positive electrode active material capable of occluding and releasing metal ions and a negative electrode having a negative electrode active material capable of occluding and releasing metal ions, and is characterized by comprising the electrolyte solution of any one of the embodiments of the present application.
1. Electrolyte solution
The electrolyte used in the electrochemical device of the present application is the electrolyte of any one of the embodiments described above in the present application.
In some embodiments, the electrolyte of the electrochemical device of the present application further comprises copper ions, wherein the copper ions are present in an amount of 0.01 to 50ppm based on the total weight of the electrolyte. In some embodiments, the copper ion is present in an amount ranging from 0.01ppm, 0.05ppm, 0.1ppm, 0.5ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 7ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, or any two of these values, based on the total weight of the electrolyte.
The electrolyte used in the electrochemical device of the present application may also include other electrolytes within a range not departing from the gist of the present application.
2. Negative electrode
The materials, compositions, and methods of making the negative electrode used in the electrochemical devices of the present application may include any of the techniques disclosed in the prior art. In some embodiments, the negative electrode is the negative electrode described in U.S. patent application US9812739B, which is incorporated by reference herein in its entirety.
In some embodiments, the anode includes a current collector and an anode active material layer on the current collector. The anode active material includes a material that reversibly intercalates/deintercalates lithium ions. In some embodiments, the material that reversibly intercalates/deintercalates lithium ions includes a carbon material. In some embodiments, the carbon material may be any carbon-based negative electrode active material commonly used in lithium ion rechargeable batteries. In some embodiments, the carbon material includes, but is not limited to: crystalline carbon, amorphous carbon, or mixtures thereof. The crystalline carbon may be amorphous, platelet-shaped, spherical or fibrous natural graphite or artificial graphite. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, and the like.
In some embodiments, the anode active material layer includes an anode active material. In some embodiments, the negative electrode active material includes, but is not limited to: lithium metal, structured lithium metal, natural graphite, artificial graphite, intermediate phase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composites, li-Sn alloys, li-Sn-O alloys, sn, snO, snO 2 Lithiated TiO of spinel structure 2 -Li 4 Ti 5 O 12 A Li-Al alloy, or any combination thereof.
When the anode includes a silicon carbon compound, silicon: carbon=1:10 to 10:1, based on the total weight of the anode active material, the median particle diameter Dv50 of the silicon carbon compound is 0.1 μm to 100 μm. When the anode includes an alloy material, the anode active material layer may be formed using a method such as vapor deposition, sputtering, plating, or the like. When the anode includes lithium metal, for example, an anode active material layer is formed with a conductive skeleton having a spherical twisted shape and metal particles dispersed in the conductive skeleton. In some embodiments, the spherical twisted conductive backbone may have a porosity of 5% -85%. In some embodiments, a protective layer may also be provided on the lithium metal anode active material layer.
In some embodiments, the anode active material layer may include a binder, and optionally, a conductive material. The binder enhances the bonding of the anode active material particles to each other and the bonding of the anode active material to the current collector. In some embodiments, the adhesive includes, but is not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
In some embodiments, the conductive material includes, but is not limited to: a carbon-based material, a metal-based material, a conductive polymer, or a mixture thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from the group consisting of metal powder, metal fiber, copper, nickel, aluminum, silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, conductive metal coated polymeric substrates, and any combination thereof.
The negative electrode may be prepared by a preparation method well known in the art. For example, the anode may be obtained by: the active material, the conductive material, and the binder are mixed in a solvent to prepare an active material composition, and the active material composition is coated on a current collector. In some embodiments, the solvent may include water or the like, but is not limited thereto.
3. Positive electrode
The materials of the positive electrode used in the electrochemical device of the present application may be prepared using materials, constructions and manufacturing methods well known in the art. In some embodiments, the positive electrode of the present application may be prepared using the techniques described in US9812739B, which is incorporated herein by reference in its entirety.
In some embodiments, a positive electrode includes a current collector and a positive electrode active material layer on the current collector. The positive electrode active material includes at least one lithiated intercalation compound that reversibly intercalates and deintercalates lithium ions. In some embodiments, the positive electrode active material includes a composite oxide. In some embodiments, the composite oxide contains lithium and at least one element selected from cobalt, manganese, and nickel.
In some embodiments, the positive electrode active material is selected from lithium cobalt oxide (LiCoO) 2 ) Ternary materials of lithium Nickel Cobalt Manganese (NCM), lithium iron phosphate (LiFePO) 4 ) Lithium manganate (LiMn) 2 O 4 ) Or any combination thereof.
In some embodiments, the positive electrode active material may have a coating layer on a surface thereof, or may be mixed with another compound having a coating layer. The coating may include at least one coating element compound selected from the group consisting of an oxide of a coating element, a hydroxide of a coating element, a oxyhydroxide of a coating element, an oxycarbonate of a coating element, and a hydroxycarbonate of a coating element. The compound used for the coating may be amorphous or crystalline.
In some embodiments, the coating elements contained in the coating may include Mg, al, co, K, na, ca, si, V, sn, ge, ga, B, as, zr, F or any combination thereof. The coating layer may be applied by any method as long as the method does not adversely affect the performance of the positive electrode active material. For example, the method may include any coating method known in the art, such as spraying, dipping, and the like.
In some embodiments, the positive electrode active material includes Ti element in an amount of t×10 based on the total weight of the positive electrode active material layer 2 ppm, t is from 2 to 10, and (a+b)/t.ltoreq.35.
In some embodiments, t is 2, 3, 4, 5, 6, 7, 8, 9, 10 or a range consisting of any two of these values.
In some embodiments, (a+b)/t is 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.4, 0.3, or a range of any two of these values.
In some embodiments, the positive electrode active material layer further includes a binder, and optionally includes a conductive material. The binder enhances the bonding of the positive electrode active material particles to each other, and also enhances the bonding of the positive electrode active material to the current collector.
In some embodiments, the adhesive includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
In some embodiments, the conductive material includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from the group consisting of metal powder, metal fiber, copper, nickel, aluminum, silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the current collector may be aluminum, but is not limited thereto.
The positive electrode may be prepared by a preparation method well known in the art. For example, the positive electrode can be obtained by: the active material, the conductive material, and the binder are mixed in a solvent to prepare an active material composition, and the active material composition is coated on a current collector. In some embodiments, the solvent may include N-methylpyrrolidone, etc., but is not limited thereto.
In some embodiments, the positive electrode is manufactured by forming a positive electrode material using a positive electrode active material layer including a lithium transition metal-based compound powder and a binder on a current collector.
In some embodiments, the positive electrode active material layer may be generally fabricated by: the positive electrode material and the binder (conductive material and thickener, etc. as needed) are dry-mixed to form a sheet, the obtained sheet is pressed against the positive electrode current collector, or these materials are dissolved or dispersed in a liquid medium to form a slurry, and the slurry is applied to the positive electrode current collector and dried. In some embodiments, the material of the positive electrode active material layer includes any material known in the art.
4. Isolation film
In some embodiments, the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuit. The material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator comprises a polymer or inorganic, etc., formed from a material that is stable to the electrolyte of the present application.
For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
The surface treatment layer is arranged on at least one surface of the substrate layer, the surface treatment layer can be a polymer layer or an inorganic layer, and also can be a layer formed by mixing a polymer and an inorganic substance, the thickness ratio of the substrate layer to the surface treatment layer is 1:1-20:1, the thickness of the substrate layer is 4-14 mu m, and the thickness of the surface treatment layer is 1-5 mu m. .
The inorganic layer comprises inorganic particles and a binder, wherein the inorganic particles are selected from one or a combination of more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is selected from one or more of polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene. The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylic polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene).
4. Application of
The electrolyte according to the embodiment of the application can be used for improving the storage resistance, the normal-temperature storage capacity retention rate, the circulation, the high-temperature storage performance, the overcharge performance and the hot-box performance of a battery, and is suitable for being used in electronic equipment comprising an electrochemical device.
The application of the electrochemical device of the present application is not particularly limited, and can be used for various known applications. Such as notebook computers, pen-input computers, mobile computers, electronic book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, video recorders, liquid crystal televisions, hand-held cleaners, portable CD-players, mini-compact discs, transceivers, electronic notebooks, calculators, memory cards, portable audio recorders, radios, standby power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting fixtures, toys, game consoles, clocks, electric tools, flashlights, cameras, household large-scale batteries, or lithium-ion capacitors, etc.
The following examples of lithium ion batteries are provided for illustration of the preparation and performance of lithium ion batteries in conjunction with specific examples of electrolyte preparation and electrochemical device testing methods, and those skilled in the art will appreciate that the preparation methods described herein are merely examples and any other suitable preparation methods are within the scope of the present application.
Although illustrated as a lithium ion battery, one skilled in the art will recognize that the positive electrode materials of the present application may be used in other suitable electrochemical devices after reading the present application. Such electrochemical devices include any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors. In particular, the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
Examples
The present application will be described in further detail with reference to examples and comparative examples, but the present application is not limited to these examples unless departing from the gist thereof.
1. Lithium ion battery preparation
1) Preparation of electrolyte:
at the water content<In a 10ppm argon atmosphere glove box, ethylene carbonate (abbreviated as EC), diethyl carbonate (abbreviated as DEC) and propylene carbonate (abbreviated as PC) were uniformly mixed in a weight ratio of 3:4:3, and then a sufficiently dried lithium salt LiPF was prepared 6 Dissolving in the mixed solvent to obtain a basic electrolyte, wherein LiPF in the basic electrolyte 6 The concentration of (C) was 1mol/L. The electrolytes of the different examples and comparative examples were obtained by adding substances in different amounts as shown in the following tables to the base electrolyte. The contents of the respective substances in the electrolyte described below are calculated based on the total weight of the electrolyte.
Examples of compounds of formula I are as follows:
examples of the carboxylate compounds are as follows:
examples of compounds of formula III are as follows:
2) Preparation of positive electrode:
lithium cobalt oxide (LiCoO) 2 ) Fully stirring and mixing the mixture with acetylene black and a binder polyvinylidene fluoride (PVDF) in a weight ratio of 96:2:2 in a proper amount of N-methylpyrrolidone (NMP) solvent to form uniform anode slurry; and (3) coating the slurry on an Al foil of the positive electrode current collector, drying, cold pressing to obtain a positive electrode active material layer, and then cutting and welding the tab to obtain the positive electrode. Wherein the positive electrode active material lithium cobaltate contained Ti element, the content of Ti element was 400ppm based on the total weight of the positive electrode active material layer in the following examples and comparative examples, unless otherwise specified.
The following illustrates a preparation method of a positive electrode active material lithium cobaltate satisfying a Ti element content of 400ppm based on the total weight of the positive electrode active material layer: coCl is to be processed 2 And TiCl 4 Respectively preparing into aqueous solutions, mixing according to the active material mol ratio of 1:n (n is more than or equal to 0 and less than or equal to 0.00081787), and adding NH 3 ·HCO 3 The pH of the mixture was adjusted to 10.5 to give a precipitate. Calcining the obtained precipitate at 400deg.C for 5 hr to obtain Ti-containing C O3 O 4 . The C obtained O3 O 4 And Li (lithium) 2 CO 3 Uniformly mixing according to the mol ratio of 2:3.15, and calcining at 1000 ℃ for 8 hours to obtain LiCoO 2 . The LiCoO obtained was then subjected to 2 Adding TiO according to the mol ratio of (0.00081787-n) 2 Mixing, sintering at 800deg.C for 8 hr to obtain positive active material lithium cobalt oxide (LiCoO) 2 )。
3) Preparation of the negative electrode:
fully stirring and mixing negative electrode active material graphite, conductive agent acetylene black, binder Styrene Butadiene Rubber (SBR) and thickener sodium carboxymethylcellulose (CMC) in a proper amount of deionized water solvent according to a weight ratio of 95:2:2:1 to form uniform negative electrode slurry; and (3) coating the slurry on a Cu foil of a negative electrode current collector, drying, cold pressing to obtain a negative electrode active material layer, and then cutting and welding tabs to obtain the negative electrode.
4) Isolation film: a porous polymer film of Polyethylene (PE) of 7.5-8.5 μm is used as a base material, and Al is arranged on the base material 2 O 3 Particle layer, al 2 O 3 The particle layer thickness is 2 μm-4 μm.
5) Preparation of a lithium ion battery: and stacking the anode, the isolating film and the cathode in sequence, enabling the isolating film to be positioned between the anode and the cathode to play a role of isolation, then winding, placing the isolating film into an outer packaging foil, injecting the prepared electrolyte into a dried battery, and performing the procedures of vacuum packaging, standing, formation, shaping and the like to prepare the lithium ion battery. The electrolyte of the lithium ion battery contained Cu ions, and the content of Cu ions in the following examples and comparative examples was 4ppm unless otherwise specified.
2. Lithium ion battery performance test method
1) Overcharge test:
the battery was discharged to 3.0V at a current of 0.5C, left for 5 minutes, then charged to 6.5V at a current of 3C, and charged at a constant voltage at a voltage of 6.5V for 1h. The test (pass) is passed without firing or explosion. Five batteries were tested in each group and the number of batteries passing the test was recorded.
2) And (3) hot box test:
the cell was discharged to 3.0V at a current of 0.5C, left for 5 minutes, then charged to 4.4V at a current of 0.5C, and constant voltage to 0.05C at a voltage of 4.4V. The fully charged battery was placed in a hot box at 140℃and incubated for 60min. The test (pass) is passed without firing or explosion. Five batteries were tested in each group at the high temperature box fixed location, and the number of batteries passing the test was recorded.
3) Storage expansion test:
the battery was discharged to 4.4V at 25C with a current of 0.5C, then charged to 4.4V with a current of 0.5C, and charged to 0.05C with a constant voltage at 4.4V, and the thickness of the battery at full charge was measured with a flat plate light pressure gauge using a pressure of 700gThe degree is denoted as a 1 . The cell was placed in a 60℃oven and stored at 60℃for 21 days (21 d), the thickness after 21 days of testing being noted as b 1 The thickness expansion rate calculation formula of the battery: (b) 1 -a 1 )/a 1 ×100％。
4) Storage impedance test:
the battery was discharged to 4.4V at 25 ℃ with a current of 0.5C, charged to 4.4V with a current of 0.5C, charged to 0.05C with a constant voltage of 4.4V, placed in a 60 ℃ oven, stored for 21 days at 60 ℃ storage conditions, and the resistance value after storage was monitored using a resistivity meter and recorded.
3. Physical and chemical testing method for lithium ion battery
1) Cu ion test
The cell was discharged to 2.8V at 0.5C current, rest 5 minutes, discharged to 2.8V at 0.05C current, rest 5 minutes, and discharged to 2.8V at 0.01C current. And removing the aluminum plastic film on the outer layer of the discharged battery. And centrifuging out electrolyte in the lithium ion battery by adopting a centrifuge. And taking out the centrifuged electrolyte, placing the sample in a digestion tank with a well-coded number, weighing the sample to 0.0001g by using an electronic balance, and recording the sample weight as c (c is less than or equal to 10 g). Slowly add 10mL of concentrated HNO 3 The sample on the inner wall was flushed into the bottom of the tank and the digestion tank was gently shaken. And cleaning the water drops outside the digestion tank by dust-free paper, and putting the cleaned water drops into an acid-dispelling instrument for digestion for 20 minutes at 180 ℃. And taking down the digestion tank to cool to room temperature when the solution is steamed to 1ml to 2ml, flushing the digestion tank with ultrapure water for 3 times, pouring the liquid into a 50ml plastic volumetric flask after flushing, and shaking uniformly after constant volume. The plasma emission spectrometer (ICP) is adopted to test the sample by using a standard curve method, and the concentration of the tested sample is recorded as ρ 1 g/ml. The Cu ion calculation results were: (ρ) 1 ×50)/c。
2) Ti element test
The cell was discharged to 2.8V at 0.5C current, rest 5 minutes, to 2.8V at 0.05C current, rest 5 minutes, discharge to 2.8V at 0.01C current, rest 5 minutes, and discharge was repeated three times using 0.01C current. The battery is disassembled by wearing clean gloves, carefulThe positive electrode and the negative electrode are separated from each other and are not in contact with each other. In a glove box, the anode is soaked with high-purity DMC (dimethyl carbonate, purity is more than or equal to 99.99%) for 10 minutes, and then taken out and dried for 30 minutes. (DMC usage:>15ml/1540mm 2 wafer area). In a dry environment, a ceramic scraper is used for scraping powder>0.4g, wrapped with weighing paper. The sample was weighed to the nearest 0.0001g using an electronic balance and recorded as the weight of the sample d (d.ltoreq.0.4 g). Adding 10mL aqua regia with the mass ratio of concentrated nitric acid to concentrated hydrochloric acid being 1:1 slowly, flushing the sample on the inner wall into the tank bottom, and slightly shaking the digestion tank. And cleaning the water drops outside the digestion tank by dust-free paper, assembling the digestion device, and putting the digestion device into a microwave digestion instrument for digestion. The digestion tank was removed, the lid was rinsed 3 times with ultrapure water, and the rinse solution was poured into the digestion tank. The sample solution was shaken, slowly poured into the funnel and flowed into the volumetric flask, and the digestion tank was rinsed 3 times, 100ml was set, and shaken well. The plasma emission spectrometer (ICP) is adopted to test the sample by using a standard curve method, and the concentration of the tested sample is recorded as ρ 2 g/ml. The Ti ion calculation results are as follows: (ρ) 2 ×100)/d。
A. The electrolytes of examples 1.1 to 1.19 and comparative examples 1.1 to 1.4, in which the contents of the compound of formula I and the carboxylate compound in the electrolyte are shown in Table 1 to 1, and lithium ion batteries were prepared according to the above-described preparation methods.
TABLE 1-1
Wherein "-" represents that the substance is not added.
Tables 1-2 show the test results of the overcharge test, the hot box test of the lithium ion batteries of examples 1.1-1.19 and comparative examples 1.1-1.4.
TABLE 1-2
It can be seen from the test results of examples 1.1 to 1.19 and comparative examples 1.1 to 1.4 that the simultaneous addition of the compound of formula I and the carboxylate compound to the electrolyte can significantly improve the overcharge performance and the hot-box performance of the lithium ion battery.
B. The electrolytes of examples 1.11 and examples 2.1 to 2.12 and lithium ion batteries were prepared according to the above preparation methods, wherein the contents of the compound of formula I, the carboxylate compound and the compound of formula III in the electrolytes are shown in table 2-1. Table 2-1 shows the test results of both the overcharge test and the storage swell test of the lithium ion batteries of examples 1.11 and examples 2.1-2.12.
TABLE 2-1
Wherein "-" represents that the substance is not added.
As can be seen from the test results of examples 2.1 to 2.12 and example 1.11, the storage expansion rate of the lithium ion battery can be significantly reduced by adding the compound of formula III to the electrolyte containing the compound of formula I and the carboxylate compound. The reason is probably that the combined action of the compound of the formula I, the carboxylate compound and the compound of the formula III can further reduce the risk of oxidizing the electrolyte, improve the protection of the positive electrode and reduce the direct contact between the interface of the positive electrode active material and the electrolyte, so that the flatulence caused by the contact between the electrolyte and the positive electrode active material during high-temperature storage can be reduced.
C. The electrolytes of examples 1.11 and 3.1 to 3.7 and lithium ion batteries were prepared according to the above preparation methods, wherein the contents of the compound of formula I, the carboxylate compound, and the lithium salt additive in the electrolytes are shown in table 3-1. Table 3-1 shows the test results of the hot box test and the storage impedance test of examples 1.11 and examples 3.1-3.7 at the same time.
TABLE 3-1
Wherein "-" represents that the substance is not added.
As can be seen from the test results of examples 3.1 to 3.7 and example 1.11, the lithium salt additive LiPO was added to the electrolyte containing the compound of formula I and the carboxylate compound 2 F 2 The storage impedance of the lithium ion battery can be remarkably reduced. This is probably due to the compounds of formula I, carboxylate compounds and LiPO 2 F 2 By the combined action, liF components in the organic protective film can be increased, so that the stability of the organic protective film can be enhanced, the tolerance to high temperature can be improved, and the storage impedance can be improved.
D. The electrolytes of examples 1.11 and examples 4.1 to 4.9 and lithium ion batteries were prepared according to the above preparation methods, wherein the contents of the related substances in the electrolytes are shown in table 4-1. Table 4-1 shows both the overcharge test and the storage impedance test results for the lithium ion batteries of examples 1.11 and examples 4.1-4.9.
TABLE 4-1
Wherein "-" represents that the substance is not added.
The battery after liquid injection is subjected to high-temperature standing in the preparation process of the lithium ion battery, electrolyte in the lithium ion battery can participate in some chemical reactions in the process, trace Cu metal impurities in the negative electrode of the lithium ion battery are dissolved out, and trace Cu ions can enhance the conductivity of the electrolyte, so that the impedance is reduced. As can be seen from the test results of examples 4.1 to 4.9 and example 1.11, the electrolyte containing the compound of formula I and the carboxylate compound contains a proper amount of Cu ions, which can significantly reduce the storage resistance of the lithium ion battery.
E. The electrolytes and lithium ion batteries of examples 1.11 and examples 5.1 to 5.10 were prepared according to the above preparation methods. Table 5-1 shows the contents of the related substances in the electrolytes of examples 1.11 and examples 5.1 to 5.10, the Ti element content in the positive electrode active material layer, and the hot box test results.
TABLE 5-1
The positive electrode active material contains Ti element, so that the interface contact between the positive electrode active material and the electrolyte can be enhanced, meanwhile, the Ti element can stabilize oxygen free radicals of the positive electrode active material, reduce the contact between the oxygen free radicals and the electrolyte, reduce the oxidation reaction between the positive electrode active material and the electrolyte, and particularly accelerate the catalytic oxidation of the electrolyte when a safety test is carried out. The application adopts the combination of the compound shown in the formula I and the fluorinated carboxylic ester, has a certain protection effect on the interface of the positive electrode, enhances the oxidation resistance of the positive electrode, and further reduces the reaction between the positive electrode active material and the electrolyte by combining the doping of Ti element, thereby realizing the effect of improving the safety of the hot box. As can be seen from the test results of examples 1.11 and examples 5.1 to 5.10, the hot box improvement effect is remarkable with the increase of the Ti doping content.
F. The electrolytes of examples 1.11 and examples 6.1-6.3 and lithium ion batteries were prepared according to the above preparation methods. Table 6-1 shows the contents of the relevant substances in the electrolytes of examples 1.11 and examples 6.1 to 6.3.
TABLE 6-1
Wherein "-" represents that the substance is not added.
Table 6-2 shows the test results of the overcharge test, the hot box test, the storage expansion test, and the storage impedance test of examples 1.11 and examples 6.1 to 6.3.
TABLE 6-2
As can be seen from the test results of examples 1.11 and examples 6.1 to 6.3, the addition of the tri-nitrile compound and LiPO to the electrolyte containing the compound of formula I and the carboxylate compound was performed simultaneously 2 F 2 When the anode active material layer contains a proper amount of Ti element and the Cu ion content in the electrolyte is within a certain range, the overcharge performance and the hot box performance of the lithium ion battery can be obviously improved, and meanwhile, the storage expansion rate and the storage impedance are obviously reduced.
Reference throughout this specification to "some embodiments," "one embodiment," "another example," "an example," "a particular example," or "a partial example" means that at least one embodiment or example in the present application includes the particular feature, structure, material, or characteristic described in the embodiment or example. Thus, descriptions appearing throughout the specification, for example: "in some embodiments," "in an embodiment," "in one embodiment," "in another example," "in one example," "in a particular example," or "example," which do not necessarily reference the same embodiments or examples in this application. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples.
Although illustrative embodiments have been shown and described, it will be understood by those skilled in the art that the foregoing embodiments are not to be construed as limiting the application and that changes, substitutions and alterations of the embodiments may be made without departing from the spirit, principles and scope of the application.

Claims (4)

1. An electrochemical device includes a positive electrode including a positive electrode active material layer, and an electrolyteThe positive electrode active material layer contains a positive electrode active material, and the electrolyte contains a compound of formula I, a carboxylate compound, a compound of formula III, and LiPO 2 F 2 And copper ions;
wherein the compound of formula I comprises at least one of the following compounds:
the weight percentage of the compound of the formula I is a wt%, and a is 0.01-5 based on the total weight of the electrolyte;
wherein the carboxylate compound comprises at least one of the following compounds:
the weight percentage of the carboxylate compound is b wt%, b is 1-30, based on the total weight of the electrolyte;
wherein the compound of formula III comprises at least one of the following compounds:
the weight percent of the compound of formula III is 0.1wt% to 5wt%, based on the total weight of the electrolyte;
wherein the LiPO is based on the total weight of the electrolyte 2 F 2 The weight percentage of (2) is 0.001-0.5 wt%;
wherein the copper ion content is 0.01ppm to 50ppm based on the total weight of the electrolyte;
wherein the positive electrode active material is encapsulatedContains Ti element in an amount of t×10 based on the total weight of the positive electrode active material layer 2 ppm, t is from 2 to 10, and (a+b)/t.ltoreq.35.
2. The electrochemical device of claim 1, wherein the compound of formula III further comprises:
3. the electrochemical device of claim 1, wherein the electrolyte further comprises a lithium salt additive comprising at least one of the following lithium salts: lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium tetrafluoro-phosphate oxalate, lithium difluorooxalato borate, or lithium hexafluorocesium acid;
wherein the weight percent of the lithium salt additive is 0.001wt% to 5wt%, based on the total weight of the electrolyte.
4. An electronic device, wherein the electronic device comprises the electrochemical device according to any one of claims 1-3.
CN202010064859.4A 2020-01-20 2020-01-20 Electrolyte and electrochemical device using the same Active CN111244541B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010064859.4A CN111244541B (en) 2020-01-20 2020-01-20 Electrolyte and electrochemical device using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010064859.4A CN111244541B (en) 2020-01-20 2020-01-20 Electrolyte and electrochemical device using the same

Publications (2)

Publication Number Publication Date
CN111244541A CN111244541A (en) 2020-06-05
CN111244541B true CN111244541B (en) 2024-04-05

Family

ID=70878120

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010064859.4A Active CN111244541B (en) 2020-01-20 2020-01-20 Electrolyte and electrochemical device using the same

Country Status (1)

Country Link
CN (1) CN111244541B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022094770A1 (en) * 2020-11-03 2022-05-12 宁德新能源科技有限公司 Electrolyte, electrochemical device, and electronic device
CN112670578B (en) * 2020-12-23 2022-11-25 东莞新能源科技有限公司 Electrolyte solution, electrochemical device, and electronic device
CN112886061B (en) * 2021-01-12 2023-01-24 宁德新能源科技有限公司 Electrolyte and electrochemical device containing same
CN113921908B (en) * 2021-09-29 2024-01-30 东莞新能源科技有限公司 Electrochemical device and electronic device comprising same
CN114335734B (en) * 2022-03-16 2022-06-28 宁德新能源科技有限公司 Electrolyte solution, and electrochemical device and electronic device comprising same
CN114824482A (en) * 2022-05-16 2022-07-29 香河昆仑新能源材料股份有限公司 Non-aqueous electrolyte of lithium ion battery and lithium ion battery

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103098290A (en) * 2010-10-22 2013-05-08 三井化学株式会社 Cyclic sulfate compound, non-aqueous electrolyte solution containing same, and lithium secondary battery
JP2014222624A (en) * 2013-05-14 2014-11-27 Tdk株式会社 Nonaqueous electrolytic solution, and lithium ion secondary battery
CN105895955A (en) * 2016-06-02 2016-08-24 宁德新能源科技有限公司 Electrolyte and lithium ion battery
CN106025356A (en) * 2016-06-23 2016-10-12 宁德新能源科技有限公司 Electrolyte and lithium-ion battery comprising same
CN108242566A (en) * 2016-12-26 2018-07-03 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN109037776A (en) * 2017-06-09 2018-12-18 宁德时代新能源科技股份有限公司 Electrolyte and battery comprising same
CN109792083A (en) * 2016-07-15 2019-05-21 索尔维公司 Non-aqueous electrolyte composition
CN109860703A (en) * 2019-01-25 2019-06-07 宁德新能源科技有限公司 A kind of electrolyte and electrochemical appliance
CN110364695A (en) * 2018-04-11 2019-10-22 宁德新能源科技有限公司 Lithium ion battery
WO2019211353A1 (en) * 2018-05-04 2019-11-07 Solvay Sa Non-aqueous liquid electrolyte composition

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103098290A (en) * 2010-10-22 2013-05-08 三井化学株式会社 Cyclic sulfate compound, non-aqueous electrolyte solution containing same, and lithium secondary battery
JP2014222624A (en) * 2013-05-14 2014-11-27 Tdk株式会社 Nonaqueous electrolytic solution, and lithium ion secondary battery
CN105895955A (en) * 2016-06-02 2016-08-24 宁德新能源科技有限公司 Electrolyte and lithium ion battery
CN106025356A (en) * 2016-06-23 2016-10-12 宁德新能源科技有限公司 Electrolyte and lithium-ion battery comprising same
CN109792083A (en) * 2016-07-15 2019-05-21 索尔维公司 Non-aqueous electrolyte composition
CN108242566A (en) * 2016-12-26 2018-07-03 宁德时代新能源科技股份有限公司 Electrolyte solution and secondary battery
CN109037776A (en) * 2017-06-09 2018-12-18 宁德时代新能源科技股份有限公司 Electrolyte and battery comprising same
CN110364695A (en) * 2018-04-11 2019-10-22 宁德新能源科技有限公司 Lithium ion battery
WO2019211353A1 (en) * 2018-05-04 2019-11-07 Solvay Sa Non-aqueous liquid electrolyte composition
CN109860703A (en) * 2019-01-25 2019-06-07 宁德新能源科技有限公司 A kind of electrolyte and electrochemical appliance

Also Published As

Publication number Publication date
CN111244541A (en) 2020-06-05

Similar Documents

Publication Publication Date Title
CN111244541B (en) Electrolyte and electrochemical device using the same
CN109786824B (en) Electrolyte solution and electrochemical device using the same
CN110429335B (en) Electrolyte solution, electrochemical device and electronic device comprising same
US7169511B2 (en) Nonaqueous electrolyte solution and nonaqueous electrolyte solution secondary battery employing the same
CN111342135B (en) Electrochemical device and electronic device comprising same
CN110380120B (en) Electrolyte solution, electrochemical device and electronic device comprising the same
CN111430793B (en) Electrolyte solution, and electrochemical device and electronic device using same
CN111525191B (en) Electrolyte and electrochemical device
CN111628219A (en) Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device
CN113394455B (en) Electrochemical device and electronic device
CN111430794B (en) Electrolyte, electrochemical device and electronic device
CN112400249A (en) Electrolyte and electrochemical device
CN109830749B (en) Electrolyte and electrochemical device
CN112119530B (en) Electrolyte solution, and electrochemical device and electronic device using same
CN111261939A (en) Electrolyte solution and electrochemical device using the same
CN111697267A (en) Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device
WO2021179300A1 (en) Electrochemical device and electronic device comprising same
CN114335685A (en) Electrochemical device and electronic device comprising same
CN110854432B (en) Electrolyte solution, and electrochemical device and electronic device using same
CN112956063A (en) Electrolyte solution, and electrochemical device and electronic device comprising same
CN111740162A (en) Electrolyte solution, electrochemical device including the same, and electronic device
CN111971845A (en) Electrolyte and electrochemical device
JP7457135B2 (en) Electrolyte and electrochemical device using it
CN116508189A (en) Electrolyte and electrochemical device and electronic device including the same
CN112271327A (en) Electrolyte solution, and electrochemical device and electronic device containing the same

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