WO2017185997A1 - Electrolyte, positive electrode, preparation method therefor and lithium ion battery - Google Patents

Electrolyte, positive electrode, preparation method therefor and lithium ion battery Download PDF

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Publication number
WO2017185997A1
WO2017185997A1 PCT/CN2017/080486 CN2017080486W WO2017185997A1 WO 2017185997 A1 WO2017185997 A1 WO 2017185997A1 CN 2017080486 W CN2017080486 W CN 2017080486W WO 2017185997 A1 WO2017185997 A1 WO 2017185997A1
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Prior art keywords
positive electrode
electrolyte
group
boronic acid
additive
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PCT/CN2017/080486
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French (fr)
Chinese (zh)
Inventor
乔飞燕
王圣
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比亚迪股份有限公司
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Publication of WO2017185997A1 publication Critical patent/WO2017185997A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/42—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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

Definitions

  • the invention belongs to the field of lithium ion batteries, and particularly relates to an electrolyte, a positive electrode, a preparation method thereof and a lithium ion battery.
  • a lithium ion battery of an electrolyte includes a housing and a battery core and an electrolyte contained in the housing, and the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • lithium ions migrate from the positive electrode through the electrolyte to the negative electrode, and the flow direction is reversed during the discharge.
  • high-energy-density secondary lithium-ion batteries have become the object of attention. Therefore, some new active materials that can be used as a complete lithium-ion battery are also noted. For example, a new type of 5V high-voltage positive electrode is introduced in the prior art.
  • the improvement of the working voltage of the material directly improves the power consumption of the battery as a whole, and has great practical significance in application. At this stage, most of the lithium battery electrolyte system can only be used stably under the voltage of 4.2v and below. When the working voltage reaches 4.2v or above, the electrolyte system will undergo oxidative decomposition and the battery will not work normally. The application of high-voltage cathode materials has created a great obstacle and the battery cycle performance is reduced.
  • the above electrolyte solution also has a technical problem that the electrolyte solvent easily reacts with the positive electrode at a high potential, so that the solvent is further oxidized and decomposed to cause excessive consumption of the electrolyte solvent.
  • the object of the present invention is to solve the technical problem that the electrolyte solvent in the prior art is easily oxidatively decomposed at a high potential.
  • the present invention provides an electrolyte.
  • the electrolyte solution includes a lithium salt, an electrolyte solvent, and an additive, and the additive is a borate pina ester compound having a structure represented by the formula (1), and the structure is as follows:
  • M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  • the present invention provides a positive electrode.
  • the positive electrode includes a positive electrode current collector, a positive electrode material layer on a surface of the positive electrode current collector, and further includes a polymer film formed by polymerization of the additive on a surface of the positive electrode material layer; 1) Boronic acid pina ester compounds of the structure shown:
  • M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  • the present invention also provides a method of preparing a positive electrode. According to an embodiment of the invention, the method comprises:
  • the present invention further provides a positive electrode prepared by the above method for producing a positive electrode.
  • the present invention also provides a lithium ion battery.
  • the lithium ion battery includes a housing and a battery core and an electrolyte contained in the housing, the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the positive electrode is provided by the present invention.
  • the positive pole is provided by the present invention.
  • the boronic acid pina ester compound of the structure of the present invention by adding a boronic acid pina ester compound of the structure of the present invention to an electrolytic solution, the boronic acid pina ester compound of the structure can be polymerized on the surface of the positive electrode material layer to form a polymer film, thereby effectively blocking
  • the electrolyte reacts on the surface of the positive electrode to protect the positive electrode from damage, and at the same time protects the electrolyte solvent from oxidative decomposition at high potential, prolonging the life of the battery at high voltage.
  • the boronic acid pina ester compound having the structure of the present invention is used as a specific additive of the present invention, and such an additive preferentially undergoes electropolymerization at a potential of 3.5V to 4.5V and is deposited on the surface of the positive electrode.
  • a layer of dense polymer film which has certain flexibility, oxidation resistance, and stability, and can cover the active point of the surface of the positive electrode, which can effectively hinder the electrolyte on the surface of the positive electrode during subsequent charging and discharging.
  • the occurrence of oxidative decomposition reaction protects the electrolyte from excessive consumption, and also protects the positive electrode from damage, and also protects the electrolyte solvent from oxidative decomposition at high potential, thereby improving the life of the battery at high voltage.
  • the specific additive of the present invention can realize the application of a common electrolyte solvent in a 4.5V high voltage environment, has remarkable effects, and makes an outstanding contribution to the field.
  • the electrolyte provided by the invention is used in a battery.
  • the additive in the electrolyte is electropolymerized on the surface of the positive electrode at a potential of 3.5V-4.5V to form a polymer film, which can greatly improve Battery The cycle performance, while the additives described herein do not affect other functions of the battery system.
  • the invention provides an electrolyte.
  • the electrolyte may include a lithium salt, an electrolyte solvent, and an additive, which is a borate pina ester compound of the structure described in the present invention.
  • the additive undergoes electropolymerization at a potential of 3.5V to 4.5V, in the positive electrode.
  • a dense polymer film is formed on the surface, which effectively blocks the oxidative decomposition reaction of the electrolyte on the surface of the positive electrode, which can protect the positive electrode from damage and protect the electrolyte solvent from oxidative decomposition at high potential.
  • the additive of the present invention has significant advantages compared to the additive. In the electrolyte solvent provided in the present application, the additive described in the present application is added, and in the same application environment, a dense polymer film can also be formed on the surface of the positive electrode.
  • the additive used is a boronic acid pina ester compound of the formula (1) having the structure shown below:
  • M may be selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  • the alkyl group may be selected from one of CH 3 (CH 2 ) n -, (CH 3 ) 2 CH(CH 2 ) n1 - and (CH 3 ) 3 C(CH 2 ) n2 - Kind, wherein 0 ⁇ n ⁇ 3, 0 ⁇ n1 ⁇ 3, 0 ⁇ n2 ⁇ 3.
  • n, n1 and n2 herein represent the total number of groups in the alkyl group.
  • CH 3 (CH 2 ) n - means that the alkyl group contains a total of 1 CH 3 group, n CH 2 A group, and so on, (CH 3 ) 2 CH(CH 2 ) n1 - represents that the alkyl group contains a total of 2 CH 3 groups, n 1 CH 2 groups and 1 CH group.
  • n 0: CH 3 -;
  • n 1: CH 3 CH 2 -;
  • n 2: CH 3 CH 2 CH 2 -.
  • the haloalkyl group may be selected from the group consisting of CX 3 (CH 2 ) n3 -, CX 2 H(CH 2 ) n4 -, CH 2 X(CH 2 ) n5 -, CH 3 (CX 2 ) n6 - And one of CH 3 (CXH) n7 - wherein said X is selected from one or more of F, Cl, Br and I, 0 ⁇ n3 ⁇ 3, 0 ⁇ n4 ⁇ 3, 0 ⁇ n5 ⁇ 3, 0 ⁇ n6 ⁇ 3, 0 ⁇ n7 ⁇ 3.
  • the olefin group may be selected from (CH 2 ) n8 CH-, (CH 2 ) n9 (CH) 2 CH 3 -, (CH 2 ) 2 CHC n10 -, CH 2 (CH) 2 C One of n11 CH 3 - and (CH) 2 C n12 CH 3 -, wherein 1 ⁇ n8 ⁇ 2 , 1 ⁇ n9 ⁇ 2 , 1 ⁇ n10 ⁇ 2 , 1 ⁇ n11 ⁇ 2 , and 0 ⁇ n12 ⁇ 2.
  • the haloalkenyl group may be selected from the group consisting of (CH 2 ) n13 CX-, (CHX) n14 CH, (CX 2 ) n15 CH-, (CHX) n16 (CH) 2 CH 3 -, ( CX 2 ) n17 (CH) 2 CH 3 -, (CH 2 ) n18 (CX) 2 CH 3 -, (CH 2 ) n19 (CH) 2 CH 2 X-, (CH 2 ) n20 (CH) 2 CHX 2 -, (CH 2 ) n21 (CH) 2 CX 3 -, (CHX) 2 CHC n22 -, (CX 2 ) 2 CHC n23 -, (CH 2 ) 2 CXC n24 -, CHX(CH) 2 C n25 CH 3 -, CX 2 (CH) 2 C n26 CH 3 -, CH 2 (CX) 2 C n27 CH 3
  • the additive may be selected from the group consisting of 4-bromomethylphenylboronic acid pinacol ester, vinyl boronic acid pinacol ester, 2-fluoropyridine-4-boronic acid pinacol ester, 2-chloropyridine-4-boronic acid.
  • the specific structure is as follows:
  • the additive may be present in an amount of from 0.1 to 10% by weight based on the total mass of the electrolyte. According to a more preferred embodiment of the invention, the additive may be present in an amount of from 0.1 to 3% by weight. It should be noted that the additive of the embodiment of the present invention can form a film layer with sufficient thickness and sufficient coverage on the surface of the positive electrode, and there is no excessive additive affecting the system.
  • the lithium salt in the electrolytic solution of the embodiment of the present invention, may be contained in an amount of 10 to 20% by weight based on the total mass of the electrolyte, and the lithium salt may be present in a concentration of 0.3 to 2 mol/L.
  • the lithium salt is various lithium salts commonly used by those skilled in the art, and may be, for example, selected from the group consisting of LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiSiF 6 , LiAlCl 4 , LiBOB, LiODFB, LiCl, LiBr, LiI, LiCF 3 .
  • the invention may employ LiPF 6 as the main lithium salt.
  • the present invention may be various electrolyte solvents commonly used by those skilled in the art, and may be selected, for example, from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • MF methyl formate
  • MA methyl acetate
  • MP methyl propionate
  • EP ethyl acetate
  • 1,3-propane sultone (1, 3-PS) vinyl sulphate
  • DTD propylene sulfate
  • ES vinyl sulfite
  • PS propylene sulfite
  • ADN succinonitrile
  • SN diethyl sulfite
  • DES ester
  • BL ⁇ -butyrolactone
  • DMSO dimethyl sulfoxide
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • the content of the electrolyte solvent in the embodiment of the present invention may be 77 to 89.9 wt% based on the total mass.
  • the carbonate-based electrolyte solvent is added to the additive of the embodiment of the invention to assist the application, the electrolyte solvent can be applied in a 4.5V high-voltage environment, which has a significant effect compared with the prior art, and at the same time, the electrolyte system is more stable. Widely used, the lithium salt dissociation degree is high, the solubility of the additive is better, and the oxidative polymerization process of the additive is not affected by the solvent of the electrolyte.
  • the present invention provides a positive electrode.
  • the positive electrode includes a positive electrode current collector, a positive electrode material layer on the surface of the positive electrode current collector, and further includes a polymer film formed by electropolymerization of the additive on the surface of the positive electrode material layer; the additive is (1) The boronic acid pina ester compound of the structure shown:
  • M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  • the surface of the positive electrode material layer has a polymer film whose composition is a polymer produced by the additive of the embodiment of the invention.
  • the polymer may be formed by polymerization of the additive.
  • the polymer of the polymer film is poly-4-bromomethylphenylboronic acid pinacol ester, polyvinylboronic acid pinacol ester, poly-2-fluoropyridine-4-boronic acid pinacol ester, poly 2 -Chloropyridine-4-boronic acid pinacol ester, poly-3-fluoropyridine-4-boronic acid pinacol ester, poly-2-chloropyridine-3-boronic acid pinacol ester and poly 6-chloropyridine-2-boronic acid pinacol ester One or several.
  • the polymer film is a protective film formed on the surface of the positive electrode at an electric potential of 3.5 V to 4.5 V as an additive in the above electrolyte.
  • the present invention provides a method of producing a positive electrode.
  • the preparation method of the positive electrode includes:
  • the present invention provides a positive electrode.
  • the positive electrode is prepared by the method described above.
  • the preparation method of the lithium ion battery electrolyte is a common method of those skilled in the art, that is, the components (including the lithium salt, the electrolyte solvent and the additive) are uniformly mixed, and the manner and sequence of the mixing are not particularly limited.
  • the present invention also provides a lithium ion battery.
  • the lithium ion battery includes a housing and a battery core and an electrolyte contained in the housing, the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the electrolyte is The electrolyte provided by the embodiment of the invention is the positive electrode provided by the embodiment of the invention.
  • the positive electrode comprises a positive electrode current collector and a positive electrode material
  • the positive electrode material comprises a positive electrode active material, a conductive agent and a positive electrode binder, wherein the conductive agent and the positive electrode binder can be bonded to the positive electrode and the positive electrode which are conventionally used in the art.
  • the negative electrode includes a negative electrode current collector and a negative electrode material
  • the negative electrode material includes a negative electrode active material and a negative electrode binder, wherein the negative electrode material may further optionally include a conductive agent, which is a conventional conductive agent and may be combined with the positive electrode material layer.
  • the conductive agents are the same or different, and the negative electrode binder may be a negative electrode binder conventionally used in the art.
  • the positive electrode active material may be a spinel structure of LiNi 0.5 Mn 1.5 O 4 or a layered structure of LiNi 0.5 Mn 0.5 O 2 positive electrode material, and further preferably, the positive electrode active material may be LiNi 0.5 Mn 1.5 O 4 with spinel structure, LiNi 0.5 Mn 1.5 O 4 with spinel structure has a higher charge and discharge potential platform, and the additive of the structure of the present invention can be applied to assist the application, and the electrolyte can be wider.
  • the electrochemical window can further highlight the improvement of the high voltage performance of the electrolyte by the electrolyte additive of the present invention.
  • the anode active material may be lithium or a graphite anode, but is not limited thereto, and metal lithium may be further more preferable.
  • the electrolyte may contain an additive which is a boronic acid pina ester compound having the structure represented by the formula (1):
  • M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  • the additive in the electrolyte can be completely consumed and formed on the surface of the positive electrode.
  • a polymer film it is also possible to have a partial residue in the electrolyte.
  • the battery of the present invention can be prepared by encapsulating a positive electrode, a negative electrode and an electrolyte provided in the present application to obtain a battery, and the additive of the present invention added in the electrolyte can generate electricity in the initial stage of charging and discharging of the battery.
  • the polymerization is carried out and deposited on the surface of the positive electrode to form a polymer film.
  • the positive electrode is used to prepare a battery.
  • the preparation method of the positive electrode at this time is not particularly limited, as long as the present application can be made.
  • the additive is polymerized and deposited on the surface of the positive electrode to form a polymer film.
  • the reaction conditions are: a temperature of 20 ° C to 55 ° C and a voltage of 3.5 V to 4.5 V.
  • Ethylene carbonate (EC), diethyl carbonate (DEC), 12% by weight of lithium hexafluorophosphate (LiPF 6 ) were dissolved in 100% by weight of electrolyte solvent in an argon glove box, and then 0.1% by weight was added.
  • 4-bromomethylphenylboronic acid pinacol ester (the boronic acid pina ester of the structure represented by the formula (1) of the present invention), wherein M is 4-bromomethylbenzene, and the lithium ion battery electrolyte of the present embodiment is obtained.
  • M 4-bromomethylbenzene
  • the positive electrode active material LiNi 0.5 Mn 1.5 O 4
  • acetylene black and polyvinylidene fluoride are uniformly mixed at a ratio of 90:5:5 and then pressed onto an aluminum foil to obtain a positive electrode sheet; the lithium metal sheet is used as a negative electrode sheet;
  • the PP composite separator is an ion exchange membrane, and the electrolytic cell C1 of the present embodiment is used to form a button battery S1 by a conventional method in the art.
  • the electrolytic solution and the button cell were prepared in the same manner as in Example 1, except that 0.5% by weight of the vinyl benzoate pina ester was used in the step (1) instead of the 4-bromomethylphenylboronic acid pinamate.
  • a lithium ion battery electrolyte C2 and a button battery S2 were prepared.
  • An electrolyte and a button cell were prepared in the same manner as in Example 1, except that in step (1), 1% by weight of 2-fluoropyridine-4-boronic acid pinamate was used in place of 4-bromomethylbenzene.
  • the boronic acid pina ester is prepared to obtain a lithium ion battery electrolyte C3 and a button battery S3.
  • An electrolyte and a button cell were prepared in the same manner as in Example 1, except that in step (1), 3% by weight of 2-chloropyridine-4-boronic acid pinamate was used in place of 4-bromomethylbenzene.
  • the boronic acid pina ester is prepared to obtain a lithium ion battery electrolyte C4 and a button battery S4.
  • the electrolyte and the button cell were prepared in the same manner as in Example 1, except that 7% by weight of 2-chloropyridine-4-boronic acid pina ester was added in step (1) instead of 4-bromomethyl group.
  • the benzoyl benzoate ester is prepared to obtain a lithium ion battery electrolyte C5 and a button battery S5.
  • the electrolyte and the button cell were prepared in the same manner as in Example 1, except that 10% of 3-fluoropyridine-4-boronic acid pina ester was added in step (1) instead of 4-bromomethylphenylboronic acid. Which ester, lithium ion battery electrolyte C6 and button battery S6 were prepared.
  • the electrolyte and the button cell were prepared in the same manner as in Example 1, except that the 4-bromomethylphenylboronic acid pina ester added in the step (1) was 12% by weight (not the content range of the present application). , more than), the lithium ion battery electrolyte C7 and the button battery S7 are prepared.
  • the electrolytic solution and the button battery were prepared in the same manner as in Example 1, except that the lithium ion battery electrolyte DC1 and the button battery DS1 were prepared without using the boronic acid ester ester additive in the step (1).
  • a three-electrode test method was used.
  • a platinum plate was used as a working electrode, and a lithium plate was used as a reference electrode and a counter electrode to characterize the electropolymerization potential of the additive and the oxidative decomposition potential of the electrolyte.
  • the test results are shown in Table 1.
  • the test results are shown in Table 2.
  • the test results are shown in Table 3.
  • the polymerization potential of the additive of the present invention is at least 4.15 V and the highest is 4.30 V; the oxidative decomposition potential of the electrolyte prepared by using the specific additive of the present invention is up to 5.95 V and the lowest is 5.60 V; Lithium-ion battery prepared by electrolyte has good performance in charge and discharge performance test and cycle test, and the battery can be used normally at a high voltage of 4.5V.

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Abstract

An electrolyte, positive electrode, preparation method therefor and lithium ion battery, the electrolyte comprising a lithium salt, an electrolyte solvent and an additive, wherein the additive is a boronic acid pinacol ester compound. In the electrolyte, by means of employing a boronic acid pinacol ester compound as a specific additive, a positive electrode is protected from damage, and an electrolyte solvent is also protected from oxidative decomposition at a high potential, thus the life cycle of a battery at a high voltage is prolonged.

Description

电解液、正极及其制备方法和锂离子电池Electrolyte, positive electrode, preparation method thereof and lithium ion battery
优先权信息Priority information
本申请请求2016年4月28日向中国国家知识产权局提交的、专利申请号为201610278018.7的专利申请的优先权和权益，并且通过参照将其全文并入此处。Priority is claimed on Japanese Patent Application No. 201610278018.7, the entire disclosure of which is hereby incorporated by reference.
技术领域Technical field
本发明属于锂离子电池领域，尤其涉及电解液、正极及其制备方法和锂离子电池。The invention belongs to the field of lithium ion batteries, and particularly relates to an electrolyte, a positive electrode, a preparation method thereof and a lithium ion battery.
背景技术Background technique
自20世纪90年代至今，锂离子二次电池从诞生达到了迅速的发展。一般来说，电解液的锂离子电池包括壳体和容纳于壳体内的电芯、电解液，电芯包括正极、负极和介于正极与负极之间的隔膜。在充电过程中，锂离子从正极通过电解液迁移至负极，而在放电过程中其流向相反。近年来，高能量密度的二次锂离子电池成为人们关注的对象，因此，人们也注意到一些可以作为二次锂电池整机使用的新型活性材料，如现有技术中介绍了新型5V高压正极材料，其工作电压的提高，直接整体提高了电池的使用功率，在应用方面具有很大的现实意义。而现阶段，绝大多数的锂电池电解液体系只能在4.2v及以下的电压下稳定使用，当工作电压达到4.2v以上时，电解液体系会发生氧化分解进而使电池无法正常工作，对高压正极材料的应用形成了极大的障碍，电池循环性能降低。Since the 1990s, lithium ion secondary batteries have developed rapidly since their birth. In general, a lithium ion battery of an electrolyte includes a housing and a battery core and an electrolyte contained in the housing, and the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. During the charging process, lithium ions migrate from the positive electrode through the electrolyte to the negative electrode, and the flow direction is reversed during the discharge. In recent years, high-energy-density secondary lithium-ion batteries have become the object of attention. Therefore, some new active materials that can be used as a complete lithium-ion battery are also noted. For example, a new type of 5V high-voltage positive electrode is introduced in the prior art. The improvement of the working voltage of the material directly improves the power consumption of the battery as a whole, and has great practical significance in application. At this stage, most of the lithium battery electrolyte system can only be used stably under the voltage of 4.2v and below. When the working voltage reaches 4.2v or above, the electrolyte system will undergo oxidative decomposition and the battery will not work normally. The application of high-voltage cathode materials has created a great obstacle and the battery cycle performance is reduced.
上述电解液还存在电解液溶剂易在高电位下与正极发生副反应，使得溶剂进一步被氧化分解导致电解液溶剂过度消耗的技术问题。The above electrolyte solution also has a technical problem that the electrolyte solvent easily reacts with the positive electrode at a high potential, so that the solvent is further oxidized and decomposed to cause excessive consumption of the electrolyte solvent.
发明内容Summary of the invention
本发明的目的是为了解决现有技术中电解液溶剂在高电位下易被氧化分解的技术问题。The object of the present invention is to solve the technical problem that the electrolyte solvent in the prior art is easily oxidatively decomposed at a high potential.
根据本发明的一个方法，本发明提供了一种电解液。根据本发明的实施例，该电解液包括锂盐、电解液溶剂和添加剂，所述添加剂为式(1)所示结构的硼酸频哪酯类化合物，其结构如下：According to one method of the present invention, the present invention provides an electrolyte. According to an embodiment of the present invention, the electrolyte solution includes a lithium salt, an electrolyte solvent, and an additive, and the additive is a borate pina ester compound having a structure represented by the formula (1), and the structure is as follows:
Figure PCTCN2017080486-appb-000001
Figure PCTCN2017080486-appb-000001
其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。 Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
根据本发明的又一方面，本发明提供了一种正极。根据本发明的实施例，该正极包括正极集流体、位于正极集流体表面的正极材料层，还包括位于正极材料层表面的由所述添加剂发生聚合反应形成的聚合物膜；所述添加剂为(1)所示结构的硼酸频哪酯类化合物：According to still another aspect of the present invention, the present invention provides a positive electrode. According to an embodiment of the present invention, the positive electrode includes a positive electrode current collector, a positive electrode material layer on a surface of the positive electrode current collector, and further includes a polymer film formed by polymerization of the additive on a surface of the positive electrode material layer; 1) Boronic acid pina ester compounds of the structure shown:
Figure PCTCN2017080486-appb-000002
Figure PCTCN2017080486-appb-000002
其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
根据本发明的再一方面，本发明还提出了一种正极的制备方法。根据本发明的实施例，该方法包括：According to still another aspect of the present invention, the present invention also provides a method of preparing a positive electrode. According to an embodiment of the invention, the method comprises:
(1)在正极集流体表明形成正极材料层；(1) forming a positive electrode material layer at the positive current collector;
(2)将权利要求1-9任意一项所述的电解液与正极材料层表面接触，接触时的电压为3.5V-4.5V。(2) The electrolytic solution according to any one of claims 1 to 9 is brought into contact with the surface of the positive electrode material layer, and the voltage at the time of contact is 3.5 V to 4.5 V.
根据本发明的又一方面，本发明进一步提出了一种由上述正极的制备方法制备得到的正极。According to still another aspect of the present invention, the present invention further provides a positive electrode prepared by the above method for producing a positive electrode.
根据本发明的又一方面，本发明还提供了一种锂离子电池。根据本发明的实施例，该锂离子电池包括壳体和容纳于壳体内的电芯、电解液，电芯包括正极、负极和介于正极与负极之间的隔膜，所述正极为本发明提供的正极。According to still another aspect of the present invention, the present invention also provides a lithium ion battery. According to an embodiment of the present invention, the lithium ion battery includes a housing and a battery core and an electrolyte contained in the housing, the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the positive electrode is provided by the present invention. The positive pole.
本发明通过在电解液中添加本发明所述结构的硼酸频哪酯类化合物，该结构的硼酸频哪酯类化合物能够在正极材料层的表面发生聚合反应形成聚合物膜，因此能够有效阻断电解液在正极表面发生副反应，可以保护正极不被损坏，同时保护电解液溶剂在高电位下不被氧化分解，延长电池在高电压下的寿命。In the present invention, by adding a boronic acid pina ester compound of the structure of the present invention to an electrolytic solution, the boronic acid pina ester compound of the structure can be polymerized on the surface of the positive electrode material layer to form a polymer film, thereby effectively blocking The electrolyte reacts on the surface of the positive electrode to protect the positive electrode from damage, and at the same time protects the electrolyte solvent from oxidative decomposition at high potential, prolonging the life of the battery at high voltage.
发明人经过大量实验发现，采用本发明所述结构的硼酸频哪酯类化合物作为本发明特定的添加剂，此类添加剂优先在3.5V-4.5V电位下发生电聚合反应，并在正极表面沉积形成一层致密的聚合物膜层，该聚合物膜具有一定柔性，耐氧化性，以及稳定性，同时能够将正极表面的活性点遮盖，可有效阻碍电解液在后续的充放电过程中在正极表面的发生的氧化分解反应，保护电解液不被过度消耗，亦可保护正极不被损坏，同时也保护电解液溶剂在高电位下不被氧化分解，以此提高电池在高电压下的寿命。与现有技术的添加剂相比较，本发明特定的添加剂可实现将普通的电解液溶剂应用在4.5V高电压环境中，具有显著的效果，对本领域做出突出的贡献。The inventors have found through extensive experiments that the boronic acid pina ester compound having the structure of the present invention is used as a specific additive of the present invention, and such an additive preferentially undergoes electropolymerization at a potential of 3.5V to 4.5V and is deposited on the surface of the positive electrode. a layer of dense polymer film, which has certain flexibility, oxidation resistance, and stability, and can cover the active point of the surface of the positive electrode, which can effectively hinder the electrolyte on the surface of the positive electrode during subsequent charging and discharging. The occurrence of oxidative decomposition reaction protects the electrolyte from excessive consumption, and also protects the positive electrode from damage, and also protects the electrolyte solvent from oxidative decomposition at high potential, thereby improving the life of the battery at high voltage. Compared with the prior art additives, the specific additive of the present invention can realize the application of a common electrolyte solvent in a 4.5V high voltage environment, has remarkable effects, and makes an outstanding contribution to the field.
将本发明提供的电解液用于电池中，在电池的充放电过程中，电解液中的添加剂在3.5V-4.5V电位下，在正极表面发生电聚合反应，形成聚合物膜，能够大大提高电池 的循环性能，同时，本发明所述的添加剂对电池体系的其他功能不构成影响。The electrolyte provided by the invention is used in a battery. During the charging and discharging process of the battery, the additive in the electrolyte is electropolymerized on the surface of the positive electrode at a potential of 3.5V-4.5V to form a polymer film, which can greatly improve Battery The cycle performance, while the additives described herein do not affect other functions of the battery system.
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。The additional aspects and advantages of the invention will be set forth in part in the description which follows.
发明详细描述Detailed description of the invention
下面详细描述本发明的实施例，下面的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。The embodiments of the present invention are described in detail below, and the following examples are intended to be illustrative only and not to limit the invention.
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下对本发明进行进一步详细说明。In order to make the technical problems, technical solutions and advantageous effects of the present invention more clear, the present invention will be further described in detail below.
根据本发明的一个方面，本发明提供了一种电解液。根据本发明的实施例，该电解液可包括锂盐、电解液溶剂和添加剂，所述添加剂为本发明所述结构的硼酸频哪酯类化合物。According to one aspect of the invention, the invention provides an electrolyte. According to an embodiment of the present invention, the electrolyte may include a lithium salt, an electrolyte solvent, and an additive, which is a borate pina ester compound of the structure described in the present invention.
本发明实施例的电解液中，通过采用本发明所述结构的硼酸频哪酯类化合物作为本发明所述电解液的添加剂，该添加剂在3.5V-4.5V电位下发生电聚合反应，在正极表面形成一层致密的聚合物膜，有效地阻断了电解液在正极表面发生的氧化分解反应，可以保护正极不被损坏，同时也保护电解液溶剂在高电位下不被氧化分解，与普通添加剂相比较，本发明添加剂具有显著的优越性。在本申请提供的电解液溶剂中，添加本申请所述的添加剂，在相同的应用环境中，同样可以在正极表面形成一层致密的聚合物膜。In the electrolytic solution of the embodiment of the present invention, by using the boric acid pina ester compound having the structure of the present invention as an additive of the electrolyte solution of the present invention, the additive undergoes electropolymerization at a potential of 3.5V to 4.5V, in the positive electrode. A dense polymer film is formed on the surface, which effectively blocks the oxidative decomposition reaction of the electrolyte on the surface of the positive electrode, which can protect the positive electrode from damage and protect the electrolyte solvent from oxidative decomposition at high potential. The additive of the present invention has significant advantages compared to the additive. In the electrolyte solvent provided in the present application, the additive described in the present application is added, and in the same application environment, a dense polymer film can also be formed on the surface of the positive electrode.
本发明的一些实施例中，所采用的添加剂为式(1)所示结构的硼酸频哪酯类化合物，具有如下所示结构：In some embodiments of the present invention, the additive used is a boronic acid pina ester compound of the formula (1) having the structure shown below:
Figure PCTCN2017080486-appb-000003
Figure PCTCN2017080486-appb-000003
其中，M可以选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M may be selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
根据本发明的优选实施例，烷基可以选自CH3(CH2)n-、(CH3)2CH(CH2)n1-和(CH3)3C(CH2)n2-中的一种，其中0≤n≤3，0≤n1≤3，0≤n2≤3。According to a preferred embodiment of the invention, the alkyl group may be selected from one of CH 3 (CH 2 ) n -, (CH 3 ) 2 CH(CH 2 ) n1 - and (CH 3 ) 3 C(CH 2 ) n2 - Kind, wherein 0≤n≤3, 0≤n1≤3, 0≤n2≤3.
需要进一步说明的是，本文中n、n1和n2代表烷基中各基团的总数，例如，CH3(CH2)n-表示该烷基中共含有1个CH3基团，n个CH2基团，以此类推，(CH3)2CH(CH2)n1-表示该烷基中共含有2个CH3基团，n1个CH2基团和1个CH基团。It should be further noted that n, n1 and n2 herein represent the total number of groups in the alkyl group. For example, CH 3 (CH 2 ) n - means that the alkyl group contains a total of 1 CH 3 group, n CH 2 A group, and so on, (CH 3 ) 2 CH(CH 2 ) n1 - represents that the alkyl group contains a total of 2 CH 3 groups, n 1 CH 2 groups and 1 CH group.
下面对上述烷基的结构式进行解释说明，具体如下：The structural formula of the above alkyl group will be explained below, as follows:
CH3(CH2)n-，当0≤n≤3时，其化学结构具体如下：CH 3 (CH 2 ) n -, when 0 ≤ n ≤ 3 , its chemical structure is as follows:
n＝0：CH3-； n=0: CH 3 -;
n＝1：CH3CH2-； n = 1: CH 3 CH 2 -;
n＝2：CH3CH2CH2-。根据本发明的优选实施例，卤代烷基可以选自CX3(CH2)n3-、CX2H(CH2)n4-、CH2X(CH2)n5-、CH3(CX2)n6-和CH3(CXH)n7-中的一种，其中，所述X选自F、Cl、Br和I中的一种或几种，0≤n3≤3，0≤n4≤3，0≤n5≤3，0≤n6≤3，0≤n7≤3。该卤代烷基的结构与上述烷基的结构类似，在此不再赘述。根据本发明的优选实施例，烯烃基可以选自(CH2)n8CH-、(CH2)n9(CH)2CH3-、(CH2)2CHCn10-、CH2(CH)2Cn11CH3-和(CH)2Cn12CH3-中的一种，其中1≤n8≤2，1≤n9≤2，1≤n10≤2，1≤n11≤2，0≤n12≤2。n=2: CH 3 CH 2 CH 2 -. According to a preferred embodiment of the invention, the haloalkyl group may be selected from the group consisting of CX 3 (CH 2 ) n3 -, CX 2 H(CH 2 ) n4 -, CH 2 X(CH 2 ) n5 -, CH 3 (CX 2 ) n6 - And one of CH 3 (CXH) n7 - wherein said X is selected from one or more of F, Cl, Br and I, 0 ≤ n3 ≤ 3, 0 ≤ n4 ≤ 3, 0 ≤ n5 ≤ 3, 0 ≤ n6 ≤ 3, 0 ≤ n7 ≤ 3. The structure of the haloalkyl group is similar to that of the above alkyl group, and will not be described herein. According to a preferred embodiment of the present invention, the olefin group may be selected from (CH 2 ) n8 CH-, (CH 2 ) n9 (CH) 2 CH 3 -, (CH 2 ) 2 CHC n10 -, CH 2 (CH) 2 C One of n11 CH 3 - and (CH) 2 C n12 CH 3 -, wherein 1 ≤ n8 ≤ 2 , 1 ≤ n9 ≤ 2 , 1 ≤ n10 ≤ 2 , 1 ≤ n11 ≤ 2 , and 0 ≤ n12 ≤ 2.
下面对上述烷基的结构式进行解释说明，具体如下：The structural formula of the above alkyl group will be explained below, as follows:
(CH2)n8CH-，当1≤n8≤2时，其化学结构具体如下：(CH 2 ) n8 CH-, when 1≤n8≤2, the chemical structure is as follows:
n8＝1：CH2＝CH-；N8=1: CH 2 =CH-;
n8＝2：CH2＝CH-CH2-。 n8 = 2: CH 2 = CH -CH 2 -.
(CH2)n9(CH)2CH3-，当1≤n9≤2，时，其化学结构具体如下：(CH 2 ) n9 (CH) 2 CH 3 -, when 1 ≤ n9 ≤ 2 , the chemical structure is as follows:
n9＝1：
Figure PCTCN2017080486-appb-000004
N9=1:
Figure PCTCN2017080486-appb-000004
n9＝2：CH3-CH＝CH-CH2-CH2-。N9=2: CH 3 -CH=CH-CH 2 -CH 2 -.
(CH2)2CHCn10-，当1≤n10≤2，时，其化学结构具体如下：(CH 2 ) 2 CHC n10 -, when 1 ≤ n10 ≤ 2 , the chemical structure is as follows:
n10＝1：
Figure PCTCN2017080486-appb-000005
N10=1:
Figure PCTCN2017080486-appb-000005
n10＝2：
Figure PCTCN2017080486-appb-000006
N10=2:
Figure PCTCN2017080486-appb-000006
CH2(CH)2Cn11CH3-，当1≤n11≤2，时，其化学结构具体如下：CH 2 (CH) 2 C n11 CH 3 -, when 1 ≤ n11 ≤ 2 , the chemical structure is as follows:
n11＝1：
Figure PCTCN2017080486-appb-000007
N11=1:
Figure PCTCN2017080486-appb-000007
n11＝2：
Figure PCTCN2017080486-appb-000008
N11=2:
Figure PCTCN2017080486-appb-000008
(CH)2Cn12CH3-，当1≤n12≤2，时，其化学结构具体如下：(CH) 2 C n12 CH 3 -, when 1 ≤ n12 ≤ 2 , the chemical structure is as follows:
n12＝1：
Figure PCTCN2017080486-appb-000009
N12=1:
Figure PCTCN2017080486-appb-000009
n12＝2
Figure PCTCN2017080486-appb-000010
N12=2
Figure PCTCN2017080486-appb-000010
根据本发明的优选实施例，卤代烯烃基可以选自(CH2)n13CX-、(CHX)n14CH、(CX2)n15CH-、(CHX)n16(CH)2CH3-、(CX2)n17(CH)2CH3-、(CH2)n18(CX)2CH3-、(CH2)n19(CH)2CH2X-、(CH2)n20(CH)2CHX2-、(CH2)n21(CH)2CX3-、(CHX)2CHCn22-、(CX2)2CHCn23-、(CH2)2CXCn24-、CHX(CH)2Cn25CH3-、CX2(CH)2Cn26CH3-、CH2(CX)2Cn27CH3-、CH2(CH)2Cn28CHX2-、CH2(CH)2Cn29CH2X-、CH2(CH)2Cn30CX3-、(CX)2Cn31CH3-、(CH)2Cn32CHX2-、(CH)2Cn33CH2X-和(CH)2Cn34CX3-中的一种，其中，所述X选自F、Cl、Br、I中的一种或几种，1≤n13≤2，1≤n14≤2，1≤n15≤2，1≤n16≤2，1≤n17≤2，1≤n18≤2，1≤n19≤2，1≤n20≤2，1≤n21≤2，1≤n22≤2，1≤n23≤2，1≤n24≤2，1≤n25≤2，1≤n26≤2，1≤n27≤2，1≤n28≤2，1≤n29≤2，1≤n30≤2，0≤n31≤2，0≤n32≤2，0≤n33≤2，0≤n34≤2中的一种。该卤代烯烃基的结构与上述烯烃基的结构类似，在此不再赘述。According to a preferred embodiment of the invention, the haloalkenyl group may be selected from the group consisting of (CH 2 ) n13 CX-, (CHX) n14 CH, (CX 2 ) n15 CH-, (CHX) n16 (CH) 2 CH 3 -, ( CX 2 ) n17 (CH) 2 CH 3 -, (CH 2 ) n18 (CX) 2 CH 3 -, (CH 2 ) n19 (CH) 2 CH 2 X-, (CH 2 ) n20 (CH) 2 CHX 2 -, (CH 2 ) n21 (CH) 2 CX 3 -, (CHX) 2 CHC n22 -, (CX 2 ) 2 CHC n23 -, (CH 2 ) 2 CXC n24 -, CHX(CH) 2 C n25 CH 3 -, CX 2 (CH) 2 C n26 CH 3 -, CH 2 (CX) 2 C n27 CH 3 -, CH 2 (CH) 2 C n28 CHX 2 -, CH 2 (CH) 2 C n29 CH 2 X- , CH 2 (CH) 2 C n30 CX 3 -, (CX) 2 C n31 CH 3 -, (CH) 2 C n32 CHX 2 -, (CH) 2 C n33 CH 2 X- and (CH) 2 C n34 One of CX 3 - wherein said X is selected from one or more of F, Cl, Br, I, 1 ≤ n13 ≤ 2, 1 ≤ n14 ≤ 2, 1 ≤ n15 ≤ 2, 1 ≤ N16≤2,1≤n17≤2,1≤n18≤2,1≤n19≤2,1≤n20≤2,1≤n21≤2,1≤n22≤2,1≤n23≤2,1≤n24≤ 2,1≤n25≤2,1≤n26≤2,1≤n27≤2,1≤n28≤2,1≤n29≤2,1≤n30≤2, 0≤n31≤2, 0≤n32≤2, One of 0 ≤ n33 ≤ 2, 0 ≤ n34 ≤ 2. The structure of the halogenated alkene group is similar to that of the above olefin group, and will not be described herein.
根据本发明的优选实施例，添加剂可以选自4-溴甲基苯硼酸频哪酯、乙烯基硼酸频哪酯、2-氟吡啶-4-硼酸频哪酯、2-氯吡啶-4-硼酸频哪酯、3-氟吡啶-4-硼酸频哪酯、2-氯吡啶-3-硼酸频哪酯和6-氯吡啶-2-硼酸频哪酯中的一种或几种。具体结构如下：According to a preferred embodiment of the invention, the additive may be selected from the group consisting of 4-bromomethylphenylboronic acid pinacol ester, vinyl boronic acid pinacol ester, 2-fluoropyridine-4-boronic acid pinacol ester, 2-chloropyridine-4-boronic acid. One or more of pinacol ester, 3-fluoropyridine-4-boronic acid pinacol ester, 2-chloropyridine-3-boronic acid pinacol ester and 6-chloropyridine-2-boronic acid pinacol ester. The specific structure is as follows:
4-溴甲基苯硼酸频哪酯4-bromomethylbenzeneboronic acid pinamate
Figure PCTCN2017080486-appb-000011
Figure PCTCN2017080486-appb-000011
乙烯基硼酸频哪酯Vinyl borate
Figure PCTCN2017080486-appb-000012
Figure PCTCN2017080486-appb-000012
2-氟吡啶-4-硼酸频哪酯2-fluoropyridine-4-boronic acid pinamate
Figure PCTCN2017080486-appb-000013
Figure PCTCN2017080486-appb-000013
2-氯吡啶-4-硼酸频哪酯2-chloropyridine-4-boronic acid pinamate
Figure PCTCN2017080486-appb-000014
Figure PCTCN2017080486-appb-000014
3-氟吡啶-4-硼酸频哪酯3-fluoropyridine-4-boronic acid pinamate
Figure PCTCN2017080486-appb-000015
Figure PCTCN2017080486-appb-000015
2-氯吡啶-3-硼酸频哪酯2-chloropyridine-3-boronic acid pinamate
Figure PCTCN2017080486-appb-000016
Figure PCTCN2017080486-appb-000016
6-氯吡啶-2-硼酸频哪酯6-chloropyridine-2-boronic acid pinamate
Figure PCTCN2017080486-appb-000017
Figure PCTCN2017080486-appb-000017
根据本发明的优选实施例，以电解液总质量为基准，添加剂的含量可以为0.1～10wt％。根据本发明更优选的实施例，添加剂的含量可以为0.1～3wt％。其中，需要说明的是，本发明实施例的添加剂既能够在正极表面形成足够厚度与足够覆盖度的膜层，同时也不会有多余的添加剂对体系造成影响。According to a preferred embodiment of the invention, the additive may be present in an amount of from 0.1 to 10% by weight based on the total mass of the electrolyte. According to a more preferred embodiment of the invention, the additive may be present in an amount of from 0.1 to 3% by weight. It should be noted that the additive of the embodiment of the present invention can form a film layer with sufficient thickness and sufficient coverage on the surface of the positive electrode, and there is no excessive additive affecting the system.
根据本发明的一些优选实施例，本发明实施例的电解液中，以电解液总质量为基准，锂盐的含量可以为10～20wt％，锂盐的浓度为0.3～2mol/L。其中，锂盐为本领域技术人员常用的各种锂盐，例如可以选自LiPF6、LiClO4、LiBF4、LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、LiI、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、 Li(SO2C2F5)2N、Li(SO3CF3)2N和LiB(C2O4)2中的一种或多种混合使用。根据本发明进一步优选的方案，本发明可以采用LiPF6作为主要锂盐。According to some preferred embodiments of the present invention, in the electrolytic solution of the embodiment of the present invention, the lithium salt may be contained in an amount of 10 to 20% by weight based on the total mass of the electrolyte, and the lithium salt may be present in a concentration of 0.3 to 2 mol/L. Wherein, the lithium salt is various lithium salts commonly used by those skilled in the art, and may be, for example, selected from the group consisting of LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiSiF 6 , LiAlCl 4 , LiBOB, LiODFB, LiCl, LiBr, LiI, LiCF 3 . SO 3 , Li(CF 3 SO 2 ) 3 , Li(CF 3 CO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(SO 2 C 2 F 5 ) 2 N, Li(SO 3 CF 3 One or more of 2 N and LiB(C 2 O 4 ) 2 are used in combination. According to a further preferred aspect of the invention, the invention may employ LiPF 6 as the main lithium salt.
本发明采用本领域技术人员常用的各种电解液溶剂即可，例如可以选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、丙酸甲酯(MP)、乙酸乙酯(EP)、1，3-丙烷磺酸内酯(1，3-PS)、硫酸乙烯酯(DTD)、硫酸丙烯酯、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、己二腈(ADN)、丁二腈(SN)、亚硫酸二乙酯(DES)、γ-丁内酯(BL)、二甲基亚砜(DMSO)中的一种或几种。优选，碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)中的一种或几种，以电解液总质量为基准，本发明实施例的电解液溶剂的含量可以为77～89.9wt％。发明人在研究中发现碳酸酯系电解液溶剂在现有技术中，高电压环境下，存在电解液溶剂在正极发生氧化还原反应的问题，导致电解液溶剂在高电位下被氧化分解、正极被损坏、降低电池在高电压下的寿命。而在碳酸酯系电解液溶剂添加本发明实施例的添加剂协助应用时，可使电解液溶剂应用在4.5V高电压环境中，与现有技术相比较存在显著效果，同时，电解液体系更稳定，应用广泛，锂盐解离度高，添加剂溶解度更好，添加剂氧化聚合过程不会受到电解液溶剂的影响等优点。The present invention may be various electrolyte solvents commonly used by those skilled in the art, and may be selected, for example, from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC). , ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), 1,3-propane sultone (1, 3-PS), vinyl sulphate (DTD), propylene sulfate, vinyl sulfite (ES), propylene sulfite (PS), adiponitrile (ADN), succinonitrile (SN), diethyl sulfite One or more of ester (DES), γ-butyrolactone (BL), and dimethyl sulfoxide (DMSO). Preferably, one or more of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC), with an electrolyte The content of the electrolyte solvent in the embodiment of the present invention may be 77 to 89.9 wt% based on the total mass. The inventors found in the research that the carbonate-based electrolyte solvent is in the prior art, in the high-voltage environment, there is a problem that the electrolyte solvent undergoes a redox reaction at the positive electrode, causing the electrolyte solvent to be oxidatively decomposed at a high potential, and the positive electrode is Damage and reduce the battery life at high voltages. When the carbonate-based electrolyte solvent is added to the additive of the embodiment of the invention to assist the application, the electrolyte solvent can be applied in a 4.5V high-voltage environment, which has a significant effect compared with the prior art, and at the same time, the electrolyte system is more stable. Widely used, the lithium salt dissociation degree is high, the solubility of the additive is better, and the oxidative polymerization process of the additive is not affected by the solvent of the electrolyte.
根据本发明的又一方面，本发明提供了一种正极。根据本发明的实施例，该正极包括正极集流体、位于正极集流体表面的正极材料层，还包括位于正极材料层表面的由添加剂发生电聚合反应形成的聚合物膜；该添加剂为(1)所示结构的硼酸频哪酯类化合物：According to still another aspect of the present invention, the present invention provides a positive electrode. According to an embodiment of the present invention, the positive electrode includes a positive electrode current collector, a positive electrode material layer on the surface of the positive electrode current collector, and further includes a polymer film formed by electropolymerization of the additive on the surface of the positive electrode material layer; the additive is (1) The boronic acid pina ester compound of the structure shown:
Figure PCTCN2017080486-appb-000018
Figure PCTCN2017080486-appb-000018
其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
正极材料层表面具有聚合物膜，该聚合物膜的组成为本发明实施例的添加剂生成的聚合物。The surface of the positive electrode material layer has a polymer film whose composition is a polymer produced by the additive of the embodiment of the invention.
根据本发明的优选实施例，聚合物可以为添加剂发生聚合反应而成。根据本发明的具体实施例，聚合物膜的聚合物为聚4-溴甲基苯硼酸频哪酯、聚乙烯基硼酸频哪酯、聚2-氟吡啶-4-硼酸频哪酯、聚2-氯吡啶-4-硼酸频哪酯、聚3-氟吡啶-4-硼酸频哪酯、聚2-氯吡啶-3-硼酸频哪酯和聚6-氯吡啶-2-硼酸频哪酯中的一种或几种。According to a preferred embodiment of the invention, the polymer may be formed by polymerization of the additive. According to a specific embodiment of the present invention, the polymer of the polymer film is poly-4-bromomethylphenylboronic acid pinacol ester, polyvinylboronic acid pinacol ester, poly-2-fluoropyridine-4-boronic acid pinacol ester, poly 2 -Chloropyridine-4-boronic acid pinacol ester, poly-3-fluoropyridine-4-boronic acid pinacol ester, poly-2-chloropyridine-3-boronic acid pinacol ester and poly 6-chloropyridine-2-boronic acid pinacol ester One or several.
聚合物膜为上述电解液中的添加剂在3.5V-4.5V电位下，在正极表面形成的一层保护膜。The polymer film is a protective film formed on the surface of the positive electrode at an electric potential of 3.5 V to 4.5 V as an additive in the above electrolyte.
根据本发明的又一方面，本发明提供了一种正极的制备方法。根据本发明的实施例， 该正极的制备方法包括：According to still another aspect of the present invention, the present invention provides a method of producing a positive electrode. According to an embodiment of the invention, The preparation method of the positive electrode includes:
(1)在正极集流体表面形成正极材料层；(1) forming a positive electrode material layer on the surface of the positive current collector;
(2)将前述的电解液与正极材料层表面接触，接触时的电压为3.5V-4.5V。(2) The foregoing electrolyte solution is brought into contact with the surface of the positive electrode material layer, and the voltage at the time of contact is 3.5V-4.5V.
根据本发明的又一方面，本发明提供了一种正极。根据本发明的实施例，该正极是由上述的方法制备得到。According to still another aspect of the present invention, the present invention provides a positive electrode. According to an embodiment of the invention, the positive electrode is prepared by the method described above.
锂离子电池电解液的制备方法为本领域技术人员的常用方法，即将各组分(包括锂盐、电解液溶剂和添加剂)混合均匀即可，对混合的方式和顺序本发明均没有特殊限定。The preparation method of the lithium ion battery electrolyte is a common method of those skilled in the art, that is, the components (including the lithium salt, the electrolyte solvent and the additive) are uniformly mixed, and the manner and sequence of the mixing are not particularly limited.
根据本发明的又一方面，本发明还提供了一种锂离子电池。根据本发明的实施例，该锂离子电池包括壳体和容纳于壳体内的电芯、电解液，电芯包括正极、负极和介于正极与负极之间的隔膜，其中，该电解液为本发明实施例提供的电解液，该正极为本发明实施例提供的正极。其中，该正极包括正极集流体及正极材料，该正极材料包括正极活性物质、导电剂和正极粘结剂，其中，导电剂和正极粘结剂可以为本领域常规使用的导电剂和正极粘结剂；负极包括负极集流体和负极材料，负极材料包括负极活性物质和负极粘结剂，其中，该负极材料还可以选择性的包括导电剂，该导电剂为常规导电剂，可以与正极材料层中的导电剂相同或不同，其中，该负极粘结剂可以为本领域常规使用的负极粘结剂。According to still another aspect of the present invention, the present invention also provides a lithium ion battery. According to an embodiment of the present invention, the lithium ion battery includes a housing and a battery core and an electrolyte contained in the housing, the battery core includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the electrolyte is The electrolyte provided by the embodiment of the invention is the positive electrode provided by the embodiment of the invention. Wherein, the positive electrode comprises a positive electrode current collector and a positive electrode material, and the positive electrode material comprises a positive electrode active material, a conductive agent and a positive electrode binder, wherein the conductive agent and the positive electrode binder can be bonded to the positive electrode and the positive electrode which are conventionally used in the art. The negative electrode includes a negative electrode current collector and a negative electrode material, and the negative electrode material includes a negative electrode active material and a negative electrode binder, wherein the negative electrode material may further optionally include a conductive agent, which is a conventional conductive agent and may be combined with the positive electrode material layer. The conductive agents are the same or different, and the negative electrode binder may be a negative electrode binder conventionally used in the art.
由于负极片、正极片、隔膜的制备工艺为本领域所公知的技术，且电池的组装也为本领域所公知的技术，在此就不再赘述。Since the preparation process of the negative electrode sheet, the positive electrode sheet, and the separator is a technique well known in the art, and the assembly of the battery is also a technique well known in the art, it will not be described herein.
根据本发明实施例提出的锂离子电池，优选，正极活性物质可以为尖晶石结构的LiNi0.5Mn1.5O4或者层状结构的LiNi0.5Mn0.5O2正极材料，进一步优选，正极活性物质可以为尖晶石结构的LiNi0.5Mn1.5O4，尖晶石结构的LiNi0.5Mn1.5O4具有更高的充放电电位平台，与本发明所述结构的添加剂协助应用，可以体现电解液更宽的电化学窗口，更能够突出本发明电解液添加剂对电解液高电压性能的提升。According to the lithium ion battery proposed by the embodiment of the present invention, preferably, the positive electrode active material may be a spinel structure of LiNi 0.5 Mn 1.5 O 4 or a layered structure of LiNi 0.5 Mn 0.5 O 2 positive electrode material, and further preferably, the positive electrode active material may be LiNi 0.5 Mn 1.5 O 4 with spinel structure, LiNi 0.5 Mn 1.5 O 4 with spinel structure has a higher charge and discharge potential platform, and the additive of the structure of the present invention can be applied to assist the application, and the electrolyte can be wider. The electrochemical window can further highlight the improvement of the high voltage performance of the electrolyte by the electrolyte additive of the present invention.
根据本发明的优选实施例，负极活性物质可以为锂或者石墨负极，但不局限于此，可以进一步优选为金属锂。According to a preferred embodiment of the present invention, the anode active material may be lithium or a graphite anode, but is not limited thereto, and metal lithium may be further more preferable.
根据本发明的优选实施例，电解液中可以含有添加剂，该添加剂为式(1)所示结构的硼酸频哪酯类化合物：According to a preferred embodiment of the present invention, the electrolyte may contain an additive which is a boronic acid pina ester compound having the structure represented by the formula (1):
Figure PCTCN2017080486-appb-000019
Figure PCTCN2017080486-appb-000019
其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
根据本发明实施例的锂离子电池，电解液中添加剂最后可被完全消耗并在正极表面形 成聚合物膜，也有可能在电解液中存在部分残留。According to the lithium ion battery of the embodiment of the invention, the additive in the electrolyte can be completely consumed and formed on the surface of the positive electrode. As a polymer film, it is also possible to have a partial residue in the electrolyte.
本发明中电池的制备，可以是将本领域常规的正极、负极以及本申请提供的电解液进行封装制备得到电池，电解液中添加的本发明所述的添加剂，在电池充放电初期能够发生电聚合反应，并在正极表面沉积形成聚合物膜。The battery of the present invention can be prepared by encapsulating a positive electrode, a negative electrode and an electrolyte provided in the present application to obtain a battery, and the additive of the present invention added in the electrolyte can generate electricity in the initial stage of charging and discharging of the battery. The polymerization is carried out and deposited on the surface of the positive electrode to form a polymer film.
同时本发明的实施例中也可以是在制备得到正极材料层表面具有聚合物膜的正极后，将该正极用于制备得到电池；此时正极的制备方法不作特殊限定，只要能够使得本申请所述的添加剂发生聚合反应并在正极表面沉积形成聚合物膜即可，反应条件为：温度为20℃～55℃，电压为3.5V-4.5V。In the embodiment of the present invention, after the positive electrode having the polymer film on the surface of the positive electrode material layer is prepared, the positive electrode is used to prepare a battery. The preparation method of the positive electrode at this time is not particularly limited, as long as the present application can be made. The additive is polymerized and deposited on the surface of the positive electrode to form a polymer film. The reaction conditions are: a temperature of 20 ° C to 55 ° C and a voltage of 3.5 V to 4.5 V.
电池的其他构造及具体制备方法为本领域技术人员公知，在此不作赘述。Other configurations of the battery and specific preparation methods are well known to those skilled in the art and will not be described herein.
以下结合具体实施例对本发明的电解液及含有该电解液的锂离子电池作进一步说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。实施例及对比例中所采用原料均通过商购得到。Hereinafter, the electrolytic solution of the present invention and a lithium ion battery containing the same will be further described with reference to specific examples. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The materials used in the examples and comparative examples were all commercially available.
实施例1Example 1
(1)电解液的制备：(1) Preparation of electrolyte:
在氩气手套箱中将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、12％重量份的六氟磷酸锂(LiPF6)溶解于100％重量份的电解液溶剂中，然后加入0.1％重量份的4-溴甲基苯硼酸频哪酯(本发明式(1)所示结构的硼酸频哪酯)，其中M为4-溴甲基苯，得到本实施例的锂离子电池电解液，记为C1；Ethylene carbonate (EC), diethyl carbonate (DEC), 12% by weight of lithium hexafluorophosphate (LiPF 6 ) were dissolved in 100% by weight of electrolyte solvent in an argon glove box, and then 0.1% by weight was added. 4-bromomethylphenylboronic acid pinacol ester (the boronic acid pina ester of the structure represented by the formula (1) of the present invention), wherein M is 4-bromomethylbenzene, and the lithium ion battery electrolyte of the present embodiment is obtained. For C1;
(2)锂离子电池的制备：(2) Preparation of lithium ion battery:
将正极活性物质(LiNi0.5Mn1.5O4)、乙炔黑、聚偏氟乙烯按配比90：5：5混合均匀后压制于铝箔上，得到正极片；将金属锂片作为负极片；以PE/PP复合隔膜为离子交换膜，采用本实施例的电解液C1，采用本领域常规方法做成扣式电池S1。The positive electrode active material (LiNi 0.5 Mn 1.5 O 4 ), acetylene black, and polyvinylidene fluoride are uniformly mixed at a ratio of 90:5:5 and then pressed onto an aluminum foil to obtain a positive electrode sheet; the lithium metal sheet is used as a negative electrode sheet; The PP composite separator is an ion exchange membrane, and the electrolytic cell C1 of the present embodiment is used to form a button battery S1 by a conventional method in the art.
实施例2Example 2
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中用0.5％重量份的乙烯基硼酸频哪酯代替4-溴甲基苯硼酸频哪酯，制备得到锂离子电池电解液C2以及扣式电池S2。The electrolytic solution and the button cell were prepared in the same manner as in Example 1, except that 0.5% by weight of the vinyl benzoate pina ester was used in the step (1) instead of the 4-bromomethylphenylboronic acid pinamate. A lithium ion battery electrolyte C2 and a button battery S2 were prepared.
实施例3Example 3
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中用1％重量份的2-氟吡啶-4-硼酸频哪酯代替4-溴甲基苯硼酸频哪酯，制备得到锂离子电池电解液C3以及扣式电池S3。An electrolyte and a button cell were prepared in the same manner as in Example 1, except that in step (1), 1% by weight of 2-fluoropyridine-4-boronic acid pinamate was used in place of 4-bromomethylbenzene. The boronic acid pina ester is prepared to obtain a lithium ion battery electrolyte C3 and a button battery S3.
实施例4 Example 4
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中用3％重量份的2-氯吡啶-4-硼酸频哪酯代替4-溴甲基苯硼酸频哪酯，制备得到锂离子电池电解液C4以及扣式电池S4。An electrolyte and a button cell were prepared in the same manner as in Example 1, except that in step (1), 3% by weight of 2-chloropyridine-4-boronic acid pinamate was used in place of 4-bromomethylbenzene. The boronic acid pina ester is prepared to obtain a lithium ion battery electrolyte C4 and a button battery S4.
实施例5Example 5
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中还加入了7％重量份的2-氯吡啶-4-硼酸频哪酯代替4-溴甲基苯硼酸频哪酯，制备得到锂离子电池电解液C5以及扣式电池S5。The electrolyte and the button cell were prepared in the same manner as in Example 1, except that 7% by weight of 2-chloropyridine-4-boronic acid pina ester was added in step (1) instead of 4-bromomethyl group. The benzoyl benzoate ester is prepared to obtain a lithium ion battery electrolyte C5 and a button battery S5.
实施例6Example 6
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中加入10％的3-氟吡啶-4-硼酸频哪酯代替4-溴甲基苯硼酸频哪酯，制备得到锂离子电池电解液C6以及扣式电池S6。The electrolyte and the button cell were prepared in the same manner as in Example 1, except that 10% of 3-fluoropyridine-4-boronic acid pina ester was added in step (1) instead of 4-bromomethylphenylboronic acid. Which ester, lithium ion battery electrolyte C6 and button battery S6 were prepared.
实施例7Example 7
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中加入的4-溴甲基苯硼酸频哪酯为12％重量份(非本申请的含量范围，偏多)，制备得到锂离子电池电解液C7以及扣式电池S7。The electrolyte and the button cell were prepared in the same manner as in Example 1, except that the 4-bromomethylphenylboronic acid pina ester added in the step (1) was 12% by weight (not the content range of the present application). , more than), the lithium ion battery electrolyte C7 and the button battery S7 are prepared.
对比例1Comparative example 1
采用与实施例1相同的步骤制备电解液和扣式电池，不同之处在于：步骤(1)中不采用硼酸频哪酯类添加剂，制备得到锂离子电池电解液DC1以及扣式电池DS1。The electrolytic solution and the button battery were prepared in the same manner as in Example 1, except that the lithium ion battery electrolyte DC1 and the button battery DS1 were prepared without using the boronic acid ester ester additive in the step (1).
性能测试Performance Testing
电解液氧化分解电位测试Electrolyte oxidation decomposition potential test
应用三电极测试方法，铂片作为工作电极，锂片做参比电极和对电极进行测试，表征添加剂电聚合电位以及电解液氧化分解电位。测试结果如表1所示。A three-electrode test method was used. A platinum plate was used as a working electrode, and a lithium plate was used as a reference electrode and a counter electrode to characterize the electropolymerization potential of the additive and the oxidative decomposition potential of the electrolyte. The test results are shown in Table 1.
表1Table 1
Figure PCTCN2017080486-appb-000020
Figure PCTCN2017080486-appb-000020
Figure PCTCN2017080486-appb-000021
Figure PCTCN2017080486-appb-000021
(2)电池充放电性能测试(2) Battery charge and discharge performance test
将各实验扣式电池S1-S7、DS1在常温下以0.1mA的电流恒流充电至4.5V，然后以0.1mA恒流放电至3.0V，记录电池的放电容量和充电容量，计算充放电效率(％)＝充电容量/放电容量×100％。测试结果如表2所示。The experimental button batteries S1-S7 and DS1 were charged at a constant current of 0.1 mA to 4.5 V at a normal temperature, and then discharged at a constant current of 0.1 mA to 3.0 V, and the discharge capacity and charge capacity of the battery were recorded to calculate the charge and discharge efficiency. (%) = charge capacity / discharge capacity × 100%. The test results are shown in Table 2.
表2Table 2
Figure PCTCN2017080486-appb-000022
Figure PCTCN2017080486-appb-000022
(3)电池循环测试(3) Battery cycle test
将上述电池在常温下以200mA恒流恒压充至4.5V，充电截止电流为20mA，然后以200mA恒流放电至3.0V，记录首次充电容量和放电容量，并计算放电效率(％)；如此反复充放电循环20、40、80、100次后，记录第20、40、80、100次循环的放电容量，计算循环后容量保持率(％)＝循环100次的放电容量/首次放电容量×100％；截止电压为4.5V)。测试结果如表3所示。The above battery was charged to 4.5 V at a constant current of 200 mA at a normal temperature, the charge cut-off current was 20 mA, and then discharged at a constant current of 200 mA to 3.0 V, and the first charge capacity and discharge capacity were recorded, and the discharge efficiency (%) was calculated; After repeating the charge and discharge cycle for 20, 40, 80, and 100 cycles, the discharge capacity at the 20th, 40th, 80th, and 100th cycles was recorded, and the capacity retention rate after the cycle (%) = the discharge capacity of the cycle 100 times / the first discharge capacity × 100%; cut-off voltage is 4.5V). The test results are shown in Table 3.
表3table 3
Figure PCTCN2017080486-appb-000023
Figure PCTCN2017080486-appb-000023
由表1-3结果可以看出，本发明添加剂聚合电位最低为4.15V，最高为4.30V；采用本发明特定添加剂制备得到的电解液氧化分解电位最高为5.95V，最低为5.60V；采用上述电解液制备的锂离子电池充放电性能测试和循环测试表现良好，电池可在4.5V的高电压下的正常应用。It can be seen from the results of Table 1-3 that the polymerization potential of the additive of the present invention is at least 4.15 V and the highest is 4.30 V; the oxidative decomposition potential of the electrolyte prepared by using the specific additive of the present invention is up to 5.95 V and the lowest is 5.60 V; Lithium-ion battery prepared by electrolyte has good performance in charge and discharge performance test and cycle test, and the battery can be used normally at a high voltage of 4.5V.
尽管本发明的具体实施方式已经得到详细的描述，本领域技术人员将会理解。根据已经公开的所有教导，可以对那些细节进行各种修改和替换，这些改变均在本发明的保护范围之内。本发明的全部范围由所附权利要求及其任何等同物给出。Although specific embodiments of the invention have been described in detail, those skilled in the art will understand. Various modifications and alterations of the details are possible in light of the teachings of the invention. The full scope of the invention is given by the appended claims and any equivalents thereof.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。 In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiment", "example", "specific example", or "some examples", etc. Particular features, structures, materials or features described in the examples or examples are included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

Claims (17)

  1. 一种电解液，包括锂盐、电解液溶剂和添加剂，其特征在于，所述添加剂为式(1)所示结构的硼酸频哪酯类化合物，其结构如下：An electrolyte comprising a lithium salt, an electrolyte solvent and an additive, wherein the additive is a boronic acid pina ester compound having the structure represented by the formula (1), and the structure is as follows:
    Figure PCTCN2017080486-appb-100001
    Figure PCTCN2017080486-appb-100001
    其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  2. 根据权利要求1所述的电解液，其特征在于，所述烷基选自CH3(CH2)n-、(CH3)2CH(CH2)n1-和(CH3)3C(CH2)n2-中的一种，其中0≤n≤3，0≤n1≤3，0≤n2≤3；The electrolyte according to claim 1, wherein said alkyl group is selected from the group consisting of CH 3 (CH 2 ) n -, (CH 3 ) 2 CH(CH 2 ) n1 - and (CH 3 ) 3 C (CH) 2 ) one of n2 - wherein 0 ≤ n ≤ 3, 0 ≤ n1 ≤ 3, 0 ≤ n2 ≤ 3;
    所述卤代烷基选自CX3(CH2)n3-、CX2H(CH2)n4-、CH2X(CH2)n5-、CH3(CX2)n6-和CH3(CXH)n7-中的一种，其中，所述X选自F、Cl、Br和I中的一种或几种，0≤n3≤3，0≤n4≤3，0≤n5≤3，0≤n6≤3，0≤n7≤3；The haloalkyl group is selected from the group consisting of CX 3 (CH 2 ) n3 -, CX 2 H(CH 2 ) n4 -, CH 2 X(CH 2 ) n5 -, CH 3 (CX 2 ) n6 - and CH 3 (CXH) n7 One of the above, wherein the X is selected from one or more of F, Cl, Br, and I, 0 ≤ n3 ≤ 3, 0 ≤ n4 ≤ 3, 0 ≤ n5 ≤ 3, 0 ≤ n6 ≤ 3, 0 ≤ n7 ≤ 3;
    所述烯烃基选自(CH2)n8CH-、(CH2)n9(CH)2CH3-、(CH2)2CHCn10-、CH2(CH)2Cn11CH3-、(CH)2Cn12CH3-中的一种，其中1≤n8≤2，1≤n9≤2，1≤n10≤2，1≤n11≤2，0≤n12≤2；The olefin group is selected from the group consisting of (CH 2 ) n8 CH-, (CH 2 ) n9 (CH) 2 CH 3 -, (CH 2 ) 2 CHC n10 -, CH 2 (CH) 2 C n11 CH 3 -, (CH a kind of 2 C n12 CH 3 -, wherein 1≤n8≤2, 1≤n9≤2, 1≤n10≤2, 1≤n11≤2, 0≤n12≤2;
    所述卤代烯烃基选自(CH2)n13CX-、(CHX)n14CH-、(CX2)n15CH-、(CHX)n16(CH)2CH3-、(CX2)n17(CH)2CH3-、(CH2)n18(CX)2CH3-、(CH2)n19(CH)2CH2X-、(CH2)n20(CH)2CHX2-、(CH2)n21(CH)2CX3-、(CHX)2CHCn22-、(CX2)2CHCn23-、(CH2)2CXCn24-、CHX(CH)2Cn25CH3-、CX2(CH)2Cn26CH3-、CH2(CX)2Cn27CH3-、CH2(CH)2Cn28CHX2-、CH2(CH)2Cn29CH2X-、CH2(CH)2Cn30CX3-、(CX)2Cn31CH3-、(CH)2Cn32CHX2-、(CH)2Cn33CH2X-和(CH)2Cn34CX3-中的一种，其中，所述X选自F、Cl、Br和I中的一种或几种，1≤n13≤2，1≤n14≤2，1≤n15≤2，1≤n16≤2，1≤n17≤2，1≤n18≤2，1≤n19≤2，1≤n20≤2，1≤n21≤2，1≤n22≤2，1≤n23≤2，1≤n24≤2，1≤n25≤2，1≤n26≤2，1≤n27≤2，1≤n28≤2，1≤n29≤2，1≤n30≤2，0≤n31≤2，0≤n32≤2，0≤n33≤2，0≤n34≤2中的一种。The halogenated alkene group is selected from the group consisting of (CH 2 ) n13 CX-, (CHX) n14 CH-, (CX 2 ) n15 CH-, (CHX) n16 (CH) 2 CH 3 -, (CX 2 ) n17 (CH 2 CH 3 -, (CH 2 ) n18 (CX) 2 CH 3 -, (CH 2 ) n19 (CH) 2 CH 2 X-, (CH 2 ) n20 (CH) 2 CHX 2 -, (CH 2 ) N21 (CH) 2 CX 3 -, (CHX) 2 CHC n22 -, (CX 2 ) 2 CHC n23 -, (CH 2 ) 2 CXC n24 -, CHX(CH) 2 C n25 CH 3 -, CX 2 (CH 2 C n26 CH 3 -, CH 2 (CX) 2 C n27 CH 3 -, CH 2 (CH) 2 C n28 CHX 2 -, CH 2 (CH) 2 C n29 CH 2 X-, CH 2 (CH) 2 C n30 CX 3 -, (CX) 2 C n31 CH 3 -, (CH) 2 C n32 CHX 2 -, (CH) 2 C n33 CH 2 X- and (CH) 2 C n34 CX 3 - , wherein X is selected from one or more of F, Cl, Br and I, 1≤n13≤2, 1≤n14≤2, 1≤n15≤2, 1≤n16≤2,1≤ N17≤2,1≤n18≤2,1≤n19≤2,1≤n20≤2,1≤n21≤2,1≤n22≤2,1≤n23≤2,1≤n24≤2,1≤n25≤ 2,1≤n26≤2,1≤n27≤2,1≤n28≤2,1≤n29≤2,1≤n30≤2, 0≤n31≤2, 0≤n32≤2, 0≤n33≤2, One of 0 ≤ n34 ≤ 2.
  3. 根据权利要求1所述的电解液，其特征在于，所述添加剂选自4-溴甲基苯硼酸频哪酯、乙烯基硼酸频哪酯、2-氟吡啶-4-硼酸频哪酯、2-氯吡啶-4-硼酸频哪酯、3-氟吡啶-4-硼酸频哪酯、2-氯吡啶-3-硼酸频哪酯和6-氯吡啶-2-硼酸频哪酯中的一种或几种。The electrolyte according to claim 1, wherein said additive is selected from the group consisting of 4-bromomethylphenylboronic acid pinacol ester, vinyl boronic acid pinacol ester, 2-fluoropyridine-4-boronic acid pinacol ester, 2 -Chloropyridine-4-boronic acid pinacol ester, 3-fluoropyridine-4-boronic acid pinacol ester, 2-chloropyridine-3-boronic acid pinacol ester and 6-chloropyridine-2-boronic acid pinacol ester Or several.
  4. 根据权利要求1所述的电解液，其特征在于，以所述电解液总质量为基准，所述添加剂的含量为0.1～10wt％。The electrolytic solution according to claim 1, wherein the additive is contained in an amount of from 0.1 to 10% by weight based on the total mass of the electrolyte.
  5. 根据权利要求4所述的电解液，其特征在于，以所述电解液总质量为基准，所述添加剂的含量为0.1～3wt％。 The electrolytic solution according to claim 4, wherein the additive is contained in an amount of from 0.1 to 3% by weight based on the total mass of the electrolyte.
  6. 根据权利要求1所述的电解液，其特征在于，所述锂盐选自LiPF6、LiClO4、LiBF4、LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、LiI、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(SO2C2F5)2N、Li(SO3CF3)2N和LiB(C2O4)2中的一种或几种。The electrolyte according to claim 1, wherein the lithium salt is selected from the group consisting of LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiSiF 6 , LiAlCl 4 , LiBOB, LiODFB, LiCl, LiBr, LiI, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 3 , Li(CF 3 CO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(SO 2 C 2 F 5 ) 2 N, Li(SO 3 CF 3 One or more of 2 N and LiB(C 2 O 4 ) 2 .
  7. 根据权利要求6所述的电解液，其特征在于，以所述电解液总质量为基准，所述锂盐的含量为10～20wt％。The electrolytic solution according to claim 6, wherein the lithium salt is contained in an amount of 10 to 20% by weight based on the total mass of the electrolytic solution.
  8. 根据权利要求1所述的电解液，其特征在于，所述电解液溶剂包括碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、亚硫酸乙烯酯、亚硫酸丙烯酯、亚硫酸二乙酯、γ-丁内酯、二甲基亚砜(DMSO)、乙酸乙酯和乙酸甲酯中的一种或几种。The electrolyte according to claim 1, wherein the electrolyte solvent comprises ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, sulfurous acid. One or more of vinyl ester, propylene sulfite, diethyl sulfite, γ-butyrolactone, dimethyl sulfoxide (DMSO), ethyl acetate, and methyl acetate.
  9. 根据权利要求8所述的电解液，其特征在于，以所述电解液的总质量为基准，所述电解液溶剂的含量为77～89.9wt％。The electrolytic solution according to claim 8, wherein the electrolyte solvent content is 77 to 89.9 wt% based on the total mass of the electrolytic solution.
  10. 一种正极，包括正极集流体、位于正极集流体表面的正极材料层，其特征在于，还包括位于正极材料层表面的由所述添加剂发生聚合反应形成的聚合物膜；所述添加剂为式(1)所示结构的硼酸频哪酯类化合物：A positive electrode comprising a positive electrode current collector and a positive electrode material layer on a surface of the positive electrode current collector, further comprising a polymer film formed by polymerization of the additive on a surface of the positive electrode material layer; 1) Boronic acid pina ester compounds of the structure shown:
    Figure PCTCN2017080486-appb-100002
    Figure PCTCN2017080486-appb-100002
    其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基和卤代烯烃基中的一种。Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
  11. 据权利要求10所述的正极，其特征在于，所述聚合物膜的聚合物为聚4-溴甲基苯硼酸频哪酯、聚乙烯基硼酸频哪酯、聚2-氟吡啶-4-硼酸频哪酯、聚2-氯吡啶-4-硼酸频哪酯、聚3-氟吡啶-4-硼酸频哪酯、聚2-氯吡啶-3-硼酸频哪酯和聚6-氯吡啶-2-硼酸频哪酯中的一种或几种。The positive electrode according to claim 10, wherein the polymer of the polymer film is poly(4-bromomethylphenylboronic acid) pinacol, polyvinylboronic acid pinacol ester, poly-2-fluoropyridine-4- Bornic acid pinacol ester, poly-2-chloropyridine-4-boronic acid pinacol ester, poly-3-fluoropyridine-4-boronic acid pinacol ester, poly-2-chloropyridine-3-boronic acid pinacol ester and poly 6-chloropyridine- One or more of 2-boronic acid pinacol ester.
  12. 一种正极的制备方法，包括：A method for preparing a positive electrode, comprising:
    (1)在正极集流体表面形成正极材料层；(1) forming a positive electrode material layer on the surface of the positive current collector;
    (2)将权利要求1-9任意一项所述的电解液与所述正极材料层表面接触，接触时的电压为3.5V-4.5V。(2) The electrolytic solution according to any one of claims 1 to 9 is in contact with the surface of the positive electrode material layer, and the voltage at the time of contact is 3.5 V to 4.5 V.
  13. 一种正极，其特征在于，所述正极由权利要求12所述的方法制备得到。A positive electrode characterized in that the positive electrode is produced by the method of claim 12.
  14. 一种锂离子电池，包括壳体和容纳于壳体内的电芯、电解液，所述电芯包括正极、负极和介于所述正极与所述负极之间的隔膜，其特征在于，所述正极为权利要求10-13任意一项提供的所述正极。 A lithium ion battery includes a housing and a battery core and an electrolyte contained in the housing, the battery core including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein The positive electrode is the positive electrode provided in any one of claims 10-13.
  15. 根据权利要求14所述的锂离子电池，其特征在于，所述正极材料包括正极活性物质、导电剂、正极粘结剂，所述正极活性物质为尖晶石结构的LiNi0.5Mn1.5O4或层状结构的LiNi0.5Mn0.5O2。The lithium ion battery according to claim 14, wherein the positive electrode material comprises a positive electrode active material, a conductive agent, a positive electrode binder, and the positive electrode active material is a spinel structure of LiNi 0.5 Mn 1.5 O 4 or Layered structure of LiNi 0.5 Mn 0.5 O 2 .
  16. 根据权利要求15所述的锂离子电池，其特征在于，所述正极活性物质为LiNi0.5Mn1.5O4。The lithium ion battery according to claim 15, wherein the positive electrode active material is LiNi 0.5 Mn 1.5 O 4 .
  17. 根据权利要求14所述的锂离子电池，其特征在于，所述电解液中含有添加剂，所述添加剂为式(1)所示结构的硼酸频哪酯类化合物：The lithium ion battery according to claim 14, wherein the electrolyte contains an additive, and the additive is a boronic acid pina ester compound having a structure represented by the formula (1):
    Figure PCTCN2017080486-appb-100003
    Figure PCTCN2017080486-appb-100003
    其中，M选自苯环、苯环的一卤代物、甲苯的一卤代物、吡啶、吡啶的一卤代物、烷基、卤代烷基、烯烃基、卤代烯烃基中的一种。 Wherein M is selected from the group consisting of a benzene ring, a monohalogen of a benzene ring, a monohalogen of toluene, a monohalogen of pyridine, pyridine, an alkyl group, a halogenated alkyl group, an alkene group, and a halogenated alkene group.
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