CN113299983A - Gel electrolyte, lithium ion battery and preparation method - Google Patents

Gel electrolyte, lithium ion battery and preparation method Download PDF

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CN113299983A
CN113299983A CN202010112952.8A CN202010112952A CN113299983A CN 113299983 A CN113299983 A CN 113299983A CN 202010112952 A CN202010112952 A CN 202010112952A CN 113299983 A CN113299983 A CN 113299983A
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electrolyte
lithium
gel electrolyte
additive
solvent
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CN113299983B (en
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廖友好
李冠杰
冯芸
朱静仪
李伟善
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South China Normal University
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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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a gel electrolyte, a preparation method thereof and a lithium ion battery. The gel electrolyte comprises a polymer matrix film, a solvent, an electrolyte lithium salt and an additive, wherein the additive is 3- (trimethylsilyl) phenylboronic acid. The gel electrolyte provided by the invention is used in a lithium ion battery, can effectively improve the interface stability of the lithium ion battery under high-voltage charging and discharging conditions, inhibits the oxidative decomposition of a solvent on the surface of an electrode, and reduces the interface impedance of the battery. The cycle and rate performance of the lithium ion battery comprising the gel electrolyte are obviously improved.

Description

Gel electrolyte, lithium ion battery and preparation method
Technical Field
The invention relates to the technical field of batteries, in particular to a gel electrolyte, a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are currently the most commonly used commercial secondary batteries, have the advantages of high energy density, high output voltage, long cycle life, small self-discharge, no memory effect and the like, and are widely applied to the fields of mobile electronic devices, power batteries and the like.
Most of the traditional commercial anode materials of the lithium ion battery are lithium cobaltate (with a specific capacity of about 145mAh/g), lithium iron phosphate (with a specific capacity of about 165mAh/g) and the like, and the energy density of the lithium ion battery can not meet the requirement of people on the energy density of the secondary battery at present gradually. Improving the working voltage of the battery is a simple and effective method for solving the problem of insufficient energy density. However, the high pressure also causes other problems, such as that the conventional carbonate electrolyte easily reacts with the electrode material under the high pressure condition, so that the solvent component of the electrolyte is oxidized and decomposed to generate high-impedance and corrosive decomposition products, the impedance between the electrode material and the electrolyte or the separator is seriously increased, the cycle performance of the battery is affected, and the service life of the battery is shortened. Some conventional solutions choose to add certain additives to the electrolyte to replace or inhibit oxidative decomposition of the electrolyte solvent; for example, Nam-Soon Cho et al (Using a lithium bis (oxalato) cathode active to active electrochemical performance of high-voltage spinel LiNi0.5Mn1.5O4The method is characterized in that the method comprises the following steps of using lithium bis (oxalato) borate as an additive to a high-voltage lithium nickel manganese oxide positive electrode material at 60 ℃, and using Electrochimica Acta,2013,104:170-177.) to effectively improve the capacity retention rate of the lithium bis (oxalato) borate from 66.9 to 78.7%. However, the resistance of the additive product is high, which leads to the significant increase of the resistance of the battery during the circulation process and the obvious gradual reduction of the circulation performance. Furthermore, the electrolyte has strong fluidity and is easily diffused into the electrode material, which also causes substances generated by side reactions under high pressure conditions in the battery to be embedded into the material, destroys the original crystal lattice of the material, increases the impedance in the material, and causes capacity fading.
Disclosure of Invention
In view of the above problems, it is necessary to provide a gel electrolyte and a method for preparing the same, which can suppress decomposition of an electrolyte under high-voltage charge and discharge conditions and improve battery cycle and rate performance.
Furthermore, the invention also provides a lithium ion battery comprising the gel electrolyte, and the cycle performance and the rate performance of the lithium ion battery are obviously improved.
The invention adopts the following specific scheme.
A gel electrolyte comprising a polymer matrix film, a solvent, an electrolyte lithium salt, and an additive, the electrolyte lithium salt and the additive being dispersed in the solvent to form an electrolyte, the electrolyte comprising the electrolyte lithium salt and the additive being dispersed in the polymer matrix film, the additive being 3- (trimethylsilyl) phenylboronic acid.
In one embodiment, the content of the additive is 0.1% to 5% calculated by the sum of the mass of the solvent and the lithium salt being 100%.
In a more specific embodiment, the additive is present in an amount of 1% to 5%, based on 100% by mass of the sum of the solvent and the lithium salt.
In a more specific embodiment, the additive is present in an amount of 3% ± 0.5% calculated as 100% by mass of the sum of the solvent and the lithium salt.
In one embodiment, the solvent includes a cyclic carbonate and a linear carbonate.
In one embodiment, the mass ratio of the cyclic carbonate to the linear carbonate is (1:3) to (3: 2).
In one embodiment, the cyclic carbonate includes at least one of ethylene carbonate and propylene carbonate; the linear carbonate includes at least one of dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
In one embodiment, the concentration of the electrolyte lithium salt is 0.8mol/L to 1.2mol/L in a dispersion system in which the electrolyte lithium salt is dispersed in the solvent.
In one embodiment, the electrolyte lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonylimide, and lithium perfluoroalkylsulfonylmethylate.
In one embodiment, the polymer matrix film is a polymer matrix film formed by coating a polymer on a support, or a self-supporting polymer matrix film formed from a polymer.
In one embodiment, the polymer is selected from at least one of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, polybutyl methacrylate, polyvinyl acetate, polyvinylidene fluoride-hexafluoropropylene copolymer, poly (methyl methacrylate-acrylonitrile-vinyl acetate), poly (n-butyl methacrylate-acrylonitrile-styrene), and poly (n-butyl methacrylate-styrene).
The invention also provides a preparation method of the gel electrolyte in any one of the embodiments, which comprises the following steps:
dissolving an electrolyte lithium salt and a 3- (trimethylsilyl) phenylboronic acid additive in a solvent to form an electrolyte solution containing the 3- (trimethylsilyl) phenylboronic acid additive; dispersing the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive in a polymer matrix film to prepare the gel electrolyte.
In one embodiment, the method of forming the polymer matrix film is selected from the group consisting of phase transfer, dipping, electrospinning, or spin coating.
In one embodiment, the solvent is subjected to a purification water removal treatment, and the substance subjected to the purification water removal treatment is selected from at least one of molecular sieves, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metals and alkaline earth metals.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a gel electrolyte, wherein the gel electrolyte is arranged between the positive electrode and the negative electrode, and the gel electrolyte is the gel electrolyte in any one of the embodiments or the gel electrolyte prepared by the preparation method of the gel electrolyte in any one of the embodiments.
The gel electrolyte provided by the invention takes the polymer matrix membrane as a matrix, has higher overall mechanical stability and extremely low fluidity, is not easy to diffuse randomly, and can slow down the occurrence of side reactions between the electrode and an electrolyte solvent, so that the battery has higher electrochemical stability.
The gel electrolyte takes 3- (trimethylsilyl) phenylboronic acid as an additive, the additive can be uniformly distributed in the gel electrolyte, and when the electrode voltage is high and the oxidizing property is strong, the additive can be gradually released and is firstly oxidized by an electrode material, so that the solvent in the electrolyte is prevented from being oxidized and decomposed into high-impedance and corrosive products. The additive is oxidized to form a low-impedance product between the interfaces of the electrolyte and the electrode material, and the impedance between the interfaces can be reduced. Moreover, the additive and the oxidation product thereof can form a protective film on the surface of the gel electrolyte to isolate the electrode material from the electrolyte; the protective film and a polymer matrix film in the gel electrolyte act together to enhance the mechanical stability and the interface stability of the gel electrolyte, further reduce the occurrence of side reactions between a solvent or lithium salt in the electrolyte and an electrode material, and ensure the service life of the battery and the long cycle stability of the capacity of the battery.
The gel electrolyte has the advantages of low raw material cost, simple components, simple preparation method, easy industrialization and high practical value. The lithium ion battery including the gel electrolyte has excellent cycle stability.
Drawings
FIG. 1 shows the results of the cycle stability test of lithium ion batteries prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention.
Fig. 2 is a time-lapse current testing curve of the lithium ion batteries prepared in example 2 of the present invention and comparative examples 1 to 2, wherein 4.35V at the upper right corner is a polarization voltage condition during the time-lapse current testing.
Fig. 3 is a result of rate capability test of the lithium ion batteries prepared in example 2 of the present invention and comparative example 2.
Fig. 4 shows the results of the cycle stability test of the lithium ion batteries prepared in example 4 of the present invention and comparative example 3.
Fig. 5 is a result of rate capability test of the lithium ion batteries prepared in example 4 of the present invention and comparative example 3.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described more fully below with reference to the accompanying embodiments and effect drawings. The examples set forth preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The term "plurality" as used herein refers to two or more items.
The invention provides a gel electrolyte. The gel electrolyte comprises a polymer matrix film, a solvent, an electrolyte lithium salt and an additive, wherein the electrolyte lithium salt and the additive are dispersed in the solvent to form an electrolyte, the electrolyte comprising the electrolyte lithium salt and the additive is dispersed in the polymer matrix film, and the additive is 3- (trimethylsilyl) phenylboronic acid.
Wherein, the content of the additive is 0.1-5% calculated according to the sum of the mass of the solvent and the lithium salt as 100%.
Optionally, the content of the additive is 1% to 5% calculated by the sum of the mass of the solvent and the mass of the lithium salt being 100%. E.g., 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.5%, or 5%. Still more preferably, the additive is present in an amount of 3% ± 0.5%. The amount of the additive should not be too high, which may result in too thick a film, increased resistance and poor cycle performance.
The structure of the 3- (trimethylsilyl) phenylboronic acid is simply shown as follows:
Figure BDA0002390634290000061
the invention discovers and specifically selects the substance as gel electricityThe electrolyte additive can improve the performance of the lithium ion battery, and if the electrolyte additive is replaced by a structural similar silane phenylboronic acid substance, the similar effect can not be generated, so that the performance of the lithium ion battery is improved.
The 3- (trimethylsilyl) phenylboronic acid can be uniformly distributed in the gel electrolyte, and by virtue of low fluidity and high mechanical stability of the gel electrolyte, the substance is not easy to diffuse into the anode and cathode materials at will, so that the reduction of the battery capacity and the service life caused by embedding of an oxidation product in the anode and cathode materials is avoided.
On the other hand, the substance has a lower oxidation potential than the solvent in the gel electrolyte, so that the substance can be oxidized preferentially to the solvent in the process of facing high-voltage charge and discharge of the battery, thereby avoiding the problems of excessive high-impedance and corrosive products generated by solvent oxidation, and further avoiding the deterioration of the electrolyte solvent, the increase of interface impedance and finally the capacity attenuation and the poor cycle performance of the battery.
Moreover, the oxidation product of the substance has low impedance, and the oxidized product exists between the electrolyte and the electrode material, so that the impedance of the battery is reduced to a certain extent, the problem that the impedance of the battery is increased due to the film formation of the product after the oxidation of the traditional solvent or additive is avoided, and the rate capability of the battery is improved. Meanwhile, the substance and the oxidation product thereof can also form a layer of protective film on the surface of the gel electrolyte, and the protective film can act with a polymer matrix film in the gel electrolyte to enhance the overall mechanical stability and interface stability of the electrolyte, further reduce the occurrence of side reactions between a solvent or lithium salt in the electrolyte and an electrode material, and ensure the overall service life of the battery and the long cycle stability of the capacity of the battery.
In the gel electrolyte, the solvent may include cyclic carbonates and linear carbonates.
The solvent can play a role in dissolving the electrolyte lithium salt and the additive, and the solvent in which the electrolyte lithium salt and the additive are dissolved infiltrates the polymer matrix film so that the electrolyte lithium salt and the additive are uniformly distributed between the polymer chain segments, the lithium salt can enhance the ionic conductivity of the whole gel electrolyte, the additive can be gradually released in the high-voltage charging and discharging process of the battery, a film is formed on the surface of the gel electrolyte or between the polymer chain segments, the mechanical stability of the whole gel electrolyte is enhanced, and the contact between the solvent and an electrode material is blocked.
In order to ensure the dielectric constant and viscosity of the entire solvent, the mass ratio of the cyclic carbonate solvent to the linear carbonate solvent may be selected as appropriate, and the mass ratio of the cyclic carbonate solvent to the linear carbonate solvent is, for example, (1:3) to (3: 2).
Wherein, the cyclic carbonate solvent comprises at least one of ethylene carbonate and propylene carbonate, and the linear carbonate solvent is selected from at least one of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
The concentration of the electrolyte lithium salt also affects the viscosity of the solvent and the ionic conductivity of the final gel electrolyte, and therefore, the concentration thereof is not too high or too low. Optionally, the concentration of the electrolyte lithium salt in the solvent is 0.8mol/L to 1.2 mol/L. For example, the concentration of the electrolytic lithium salt is 0.8mol/L, 1mol/L, 1.2 mol/L.
The electrolyte lithium salt may be selected from one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonimide, and lithium perfluoroalkyl sulfonylmethide.
The polymer matrix film in the gel electrolyte mainly functions to support and contain the solvent, the electrolyte lithium salt and the additive.
Wherein the polymer is selected from at least one of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, polybutyl methacrylate, polyvinyl acetate, polyvinylidene fluoride-hexafluoropropylene copolymer, poly (methyl methacrylate-acrylonitrile-vinyl acetate), poly (n-butyl methacrylate-acrylonitrile-styrene), or poly (n-butyl methacrylate-styrene).
The polymer matrix film may be formed by coating the above-mentioned polymer on a support, or may be a self-supporting polymer matrix film formed by preparing the above-mentioned polymer. The support may be a commonly used porous polymer membrane, such as a polyethylene membrane, a polypropylene membrane, or the like.
In another aspect, the present invention also provides a method for preparing the gel electrolyte as described above, which comprises the following steps.
And step S1, coating the polymer on a support or preparing the polymer into a self-supporting film to obtain the polymer matrix film.
The polymer may be coated on the support by phase transfer method, soaking method, knife coating method, or spin coating method, so long as the polymer can be coated on the support to form the polymer matrix film.
The preparation of the polymer into the self-supporting film can be realized by adopting an electrostatic spinning method.
Step S2, dissolving electrolyte lithium salt and 3- (trimethylsilyl) phenylboronic acid additive in solvent to obtain electrolyte containing 3- (trimethylsilyl) phenylboronic acid additive.
Wherein, before dissolving the electrolyte lithium salt and the 3- (trimethylsilyl) phenylboronic acid additive, a purification and water removal treatment may be performed to remove impurities and moisture that may remain in the solvent. The substance for purifying and removing water can be at least one selected from molecular sieve, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metal or alkaline earth metal.
In this step, the contents of the electrolyte lithium salt and the additive should be controlled. For example, the concentration of the lithium salt is 1 mol/L. The content of the 3- (trimethylsilyl) phenylboronic acid additive is 0.1% to 5%, for example 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.5% or 5%, calculated as the sum of the mass of the solvent and the lithium salt being 100%.
Preferably, the additive is present in an amount of 3% ± 1%.
Step S3, mixing the polymer matrix film with the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
One of the simpler mixing methods is to immerse the polymer matrix film in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive, and take out the polymer matrix film after the polymer matrix film sufficiently adsorbs the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive. Another way of mixing is to drop an electrolyte containing a 3- (trimethylsilyl) phenylboronic acid additive into the polymer matrix film until it is saturated with adsorption. It should be understood that the manner of mixing is very wide, as long as the polymer matrix film can be filled with the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive, and the preparation process should not be limited.
The preparation process is simple, has low requirement on environment and is easy for large-scale production.
In yet another aspect, the present disclosure also provides a lithium ion battery including a positive electrode, a negative electrode, and a gel electrolyte. The gel electrolyte is arranged between the positive electrode and the negative electrode, and the gel electrolyte is the gel electrolyte provided in the above embodiment or the gel electrolyte prepared according to the above gel electrolyte preparation method.
As a specific example, the positive electrode sheet active material thereof is selected from at least one of lithium cobaltate, lithium nickel manganese oxide, layered lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, lithium iron manganese phosphate, lithium manganese oxide, and lithium nickel oxide; the negative plate can be prepared from at least one material of artificial graphite, natural graphite, mesocarbon microbeads, petroleum coke, lithium titanate and metallic lithium.
In order to facilitate understanding of the contents of the embodiments, the gel electrolyte, the method for preparing the same, and the lithium ion battery according to the present invention will be described in further detail, and specific examples and comparative examples performed according to the embodiments will be described below. The superiority of the present invention will be apparent from the effect test of each example and comparative example described below.
The following raw materials are all commercially available without specific mention.
Example 1
(1) And soaking the polyethylene diaphragm in polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) to coat the PVDF-HFP on the surface of the polyethylene diaphragm matrix to obtain the PVDF-HFP polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (3) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 1% of the mass of the common electrolyte, and thus obtaining the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained PVDF-HFP polymer matrix membrane in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 40 minutes to ensure that the electrolyte is saturated in absorption, thus obtaining the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) Adopts layered nickel cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and assembling the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Example 2
(1) And soaking the polyethylene diaphragm in polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) to coat the PVDF-HFP on the surface of the polyethylene diaphragm matrix to obtain the PVDF-HFP polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (4) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 3% of that of the common electrolyte, so as to obtain the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained PVDF-HFP polymer matrix membrane in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 40 minutes to ensure that the electrolyte is saturated in absorption, thus obtaining the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) Adopts layered nickel cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and assembling the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Example 3
(1) And soaking the polyethylene diaphragm in polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) to coat the PVDF-HFP on the surface of the polyethylene diaphragm matrix to obtain the PVDF-HFP polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (4) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 5% of that of the common electrolyte to obtain the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained PVDF-HFP polymer matrix membrane in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 40 minutes to ensure that the electrolyte is saturated in absorption, thus obtaining the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) Adopts layered nickel cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and assembling the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Example 4
(1) And soaking the polyethylene diaphragm in poly (n-butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) to coat the P (BMA-AN-St) on the surface of the polyethylene diaphragm matrix to obtain the P (BMA-AN-St) polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (4) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 3% of that of the common electrolyte, so as to obtain the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained P (BMA-AN-St) polymer matrix membrane in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 40 minutes to ensure that the electrolyte is saturated to obtain a gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) Using layered nickel cobalt lithium aluminate LiNi0.8Co0.15Al0.05O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and assembling the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Example 5
(1) And soaking the polyethylene diaphragm in poly (n-butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) to coat the P (BMA-AN-St) on the surface of the polyethylene diaphragm matrix to obtain the P (BMA-AN-St) polymer matrix film.
(2) The method comprises the following steps of mixing a cyclic carbonate solvent Ethylene Carbonate (EC) and a linear carbonate solvent Ethyl Methyl Carbonate (EMC) according to a mass ratio of EC: EMC 3: 7, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.2 mol/L;
(4) and (4) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 0.5% of that of the common electrolyte, so as to obtain the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained P (BMA-AN-St) high molecular polymer film in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 20 minutes to ensure that the electrolyte is saturated, thus obtaining the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) And (3) assembling the layered lithium manganate serving as a positive electrode material, the lithium titanate serving as a negative electrode material and the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Example 6
(1) A poly (methyl methacrylate) (PMMA) high molecular polymer was coated on a polyethylene diaphragm substrate using a phase transfer method to a PMMA polymer matrix film.
(2) The method comprises the following steps of mixing a cyclic carbonate solvent Ethylene Carbonate (EC) and a linear carbonate solvent Ethyl Methyl Carbonate (EMC) according to a mass ratio of EC: EMC 3: 7, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.2 mol/L;
(4) and (4) adding a 3- (trimethylsilyl) phenylboronic acid additive into the common electrolyte prepared in the step (3), wherein the mass of the 3- (trimethylsilyl) phenylboronic acid additive is 2% of that of the common electrolyte, so as to obtain the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(5) And (3) soaking the obtained P (BMA-AN-St) high molecular polymer film in the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive obtained in the step (4) for 30 minutes to ensure that the electrolyte is saturated, thus obtaining the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
(6) And (3) assembling lithium iron phosphate serving as a positive electrode material, lithium titanate serving as a negative electrode material and the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive.
Comparative example 1
(1) Cyclic carbonate solvent Ethylene Carbonate (EC), linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(3) using layered nickel cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and adding a proper amount of the common electrolyte prepared in the step (2) to obtain the lithium ion battery containing the common electrolyte.
Comparative example 2
(1) And soaking the polyethylene diaphragm in polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) to coat the PVDF-HFP on the surface of the polyethylene diaphragm matrix to obtain the PVDF-HFP polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (3) soaking the obtained PVDF-HFP polymer matrix membrane in the common electrolyte obtained in the step (3) for 40 minutes to ensure that the PVDF-HFP polymer matrix membrane is saturated in absorption, thus obtaining the gel electrolyte containing the common electrolyte.
(5) Adopts layered nickel cobalt lithium manganate LiNi0.8Co0.1Mn0.1O2And (3) as a positive electrode material, using metal lithium as a negative electrode material, and assembling the gel electrolyte containing the common electrolyte prepared in the step (5) to obtain the lithium ion battery containing the gel electrolyte containing the common electrolyte.
Comparative example 3
(1) And soaking the polyethylene diaphragm in poly (n-butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) to coat the P (BMA-AN-St) on the surface of the polyethylene diaphragm matrix to obtain the P (BMA-AN-St) polymer matrix film.
(2) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC: EMC: DEC ═ 3: 5: 2, mixing; purifying and removing impurities and water by adopting a molecular sieve;
(3) the ion conducting lithium salt lithium hexafluorophosphate (LiPF) is added at room temperature (25 deg.C)6) Dissolving the mixture in the solvent obtained in the step (2), and uniformly stirring to obtain a common electrolyte, wherein LiPF6The solubility is 1.0 mol/L;
(4) and (3) soaking the obtained P (BMA-AN-St) polymer matrix membrane in the common electrolyte obtained in the step (3) for 40 minutes to ensure that the absorption of the common electrolyte is saturated, thus obtaining the gel electrolyte containing the common electrolyte.
(5) Using layered nickel cobalt lithium aluminate LiNi0.8Co0.15Al0.05O2And (4) assembling the lithium ion battery containing the gel electrolyte of the common electrolyte solution by using metal lithium as a cathode material and using the gel electrolyte containing the common electrolyte solution prepared in the step (4).
When the charge and discharge performance test is carried out, the charge cut-off voltage is more than 4.2V.
FIG. 1 shows the results of the cycle stability tests of the lithium ion batteries prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2. As can be seen from the results of comparative example 1 and comparative example 2 in the figure, the cycle stability of the lithium ion battery using the gel electrolyte was better than that of the liquid electrolyte; further, as can be seen from the results of examples 1 to 3 and comparative example 2 in the figure, the cycle stability of the lithium ion battery to which the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive was added was significantly superior to that of the lithium ion battery using the gel electrolyte. In addition, the electrolyte with 3 mass percent and 5 mass percent of 3- (trimethylsilyl) phenylboronic acid has the best cycle effect corresponding to the lithium ion battery.
Fig. 2 is a chronoamperometric test of lithium ion batteries fabricated with electrolytes prepared in example 2 of the present invention and comparative examples 1 and 2. The residual current of the lithium ion battery gradually tends to be stable along with time in the test process, and the smaller the residual current is, the less the oxidative decomposition reaction is under the high voltage is. Among them, the high voltage stability of the lithium ion battery corresponding to example 2 is significantly improved compared to comparative examples 1 and 2, which shows that the oxidative decomposition reaction at high voltage is significantly suppressed by the introduction of the 3- (trimethylsilyl) phenylboronic acid additive.
Fig. 3 is a result of a rate test of the lithium ion batteries prepared in example 2 of the present invention and comparative example 2. The rate performance of example 2 is significantly better than that of comparative example 2, which shows that the introduction of the 3- (trimethylsilyl) phenylboronic acid additive effectively reduces the internal impedance of the lithium ion battery, thereby improving the rate performance of the lithium ion battery prepared in example 2.
Fig. 4 is a cycle stability test of the lithium ion batteries prepared in example 4 of the present invention and comparative example 3. Fig. 4 illustrates that the cycle stability of the lithium ion battery corresponding to the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive can be significantly improved in different polymer electrolyte systems.
Fig. 5 is a rate test of lithium ion batteries prepared in example 4 of the present invention and comparative example 3. Fig. 5 illustrates that the rate capability of the lithium ion battery corresponding to the gel electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive can be remarkably improved in different polymer electrolyte systems.
Fig. 4 and 5 can together illustrate the superiority of the action of the additive itself, which can be adapted to different polymer electrolyte systems.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A gel electrolyte comprising a polymer matrix film, a solvent, an electrolyte lithium salt and an additive, wherein said electrolyte lithium salt and said additive are dispersed in said solvent to form an electrolyte, wherein said electrolyte comprising said electrolyte lithium salt and said additive is dispersed in said polymer matrix film, and wherein said additive is 3- (trimethylsilyl) phenylboronic acid.
2. The gel electrolyte of claim 1, wherein the additive is present in an amount of 0.1% to 5% based on 100% by mass of the sum of the solvent and the electrolyte lithium salt.
3. A gel electrolyte according to claim 1 or 2, wherein the solvent comprises a cyclic carbonate and a linear carbonate.
4. The gel electrolyte of claim 3, wherein the mass ratio of the cyclic carbonate to the linear carbonate is (1:3) to (3: 2).
5. A gel electrolyte according to claim 3, wherein the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate; the linear carbonate is at least one selected from dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
6. A gel electrolyte according to any one of claims 1 to 2 and 4 to 5, wherein a concentration of the electrolyte lithium salt in the electrolyte solution is 0.8mol/L to 1.2 mol/L.
7. A gel electrolyte according to any one of claims 1 to 2 and 4 to 5, wherein the electrolyte lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonylimide and lithium perfluoroalkylsulfonylmethylate.
8. A gel electrolyte according to any one of claims 1 to 2 and 4 to 5, wherein the polymer matrix film is a polymer matrix film formed by coating a polymer on a support, or a self-supporting polymer matrix film formed by preparing a polymer;
the polymer is selected from at least one of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, polybutyl methacrylate, polyvinyl acetate, polyvinylidene fluoride-hexafluoropropylene copolymer, poly (methyl methacrylate-acrylonitrile-vinyl acetate), poly (n-butyl methacrylate-acrylonitrile-styrene), and poly (n-butyl methacrylate-styrene).
9. A method for preparing a gel electrolyte according to any one of claims 1 to 8, comprising the steps of:
dissolving an electrolyte lithium salt and a 3- (trimethylsilyl) phenylboronic acid additive in a solvent to form an electrolyte solution containing the 3- (trimethylsilyl) phenylboronic acid additive; dispersing the electrolyte containing the 3- (trimethylsilyl) phenylboronic acid additive in a polymer matrix film to prepare the gel electrolyte.
10. A lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode and a gel electrolyte, wherein the gel electrolyte is arranged between the positive electrode and the negative electrode, and the gel electrolyte is the gel electrolyte according to any one of claims 1 to 8 or the gel electrolyte prepared by the preparation method of the gel electrolyte according to claim 9.
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