CN112979873B - Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof - Google Patents
Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN112979873B CN112979873B CN202110188835.4A CN202110188835A CN112979873B CN 112979873 B CN112979873 B CN 112979873B CN 202110188835 A CN202110188835 A CN 202110188835A CN 112979873 B CN112979873 B CN 112979873B
- Authority
- CN
- China
- Prior art keywords
- lithium
- monomer
- lithium salt
- electrolyte
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a multi-copolymerization single ion polymer electrolyte and a preparation method and application thereof, wherein the multi-copolymerization single ion polymer electrolyte has a structure shown as a formula I:
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a multi-copolymerization single-ion polymer electrolyte and a preparation method and application thereof.
Background
Due to the characteristics of high energy density, light weight, rapid charge and discharge, long service life and the like, lithium ion batteries are rapidly expanding from the application fields which are originally limited to portable consumer electronics products to the application fields with strict performance requirements, such as electric vehicles, fixed large-scale energy storage or microelectronics. In the prior art, the use of liquid electrolytes has been limited due to significant safety issues, and solid electrolytes are being used instead of liquid electrolytes because they do not use solvents and have the advantage of suppressing lithium dendrites. The single-ion conductor polymer electrolyte can be used as a solid electrolyte, and comprises a polymer main chain and an anion group which can move freely and is responsible for ion migration, the special structure of the single-ion conductor polymer electrolyte can enable lithium ion migration to be stable and uniform, but the use of the single structure of the single-ion conductor polymer electrolyte cannot meet the overall requirements of a lithium ion battery on ion conductivity, an electrochemical window and other properties, monomers with different properties can be selected to be copolymerized with monomers forming a single-ion polymer generally so as to improve the properties of the prepared single-ion polymer electrolyte, but the ion conductivity, the electrochemical window and the compatibility of the existing single-ion polymer electrolyte and an electrode contact interface are still required to be further improved.
Disclosure of Invention
The invention provides a multi-copolymerization single ion polymer electrolyte which has good ionic conductivity, electrochemical window, compatibility with an electrode contact interface and other performances, and can effectively overcome the defects in the prior art.
In one aspect of the present invention, there is provided a multiple copolymerized single ion polymer electrolyte, which has a structure shown in formula I:
wherein m is an integer of 20 to 200, n is an integer of 20 to 500, k is an integer of 10 to 100, and i is 8 or 9.
The multi-copolymerization single-ion polymer electrolyte is prepared by copolymerizing lithium salt monomers containing unsaturated double bonds, ethylene vinyl carbonate and polyoxyethylene ether containing unsaturated double bonds, and the performances of the single-ion polymer electrolyte such as conductivity, electrochemical window, interface compatibility and the like can be improved by selecting monomers with different properties for copolymerization and adjusting the microstructure of the polymer electrolyte. The inventor considers through research and analysis that in the structure of the formula I, a lithium salt monomer group can provide high ionic conductivity and ion mobility coefficient for a polymer electrolyte, a vinylene carbonate group with a carbonate structure on a side chain can provide a wide electrochemical window for the polymer electrolyte, and a polyoxyethylene ether group can effectively improve the flexibility of the polymer electrolyte and an electrolyte membrane formed by the polymer electrolyte, so as to improve the interface compatibility with an electrode material, therefore, the multi-copolymerization single-ion polymer electrolyte has the performances of high ionic conductivity, wide electrochemical window, excellent interface compatibility between a positive electrode and a negative electrode and the like.
In some embodiments, m may be, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or a range of any two of these values, and n may be, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, 200, 220, 250, 280, 300, 320, 350, 380, 400, 420, 450, 480, 500, or a range of any two of these values; k may be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or a range of any two of these values.
For example, in some embodiments, the electrolyte of formula I above includes an electrolyte of the structure of formula Ia below:
in another aspect of the present invention, there is provided a method for preparing the above polyelectrolytes, comprising: copolymerizing a lithium salt monomer, ethylene carbonate and a polyoxyethylene ether monomer to obtain an electrolyte; wherein, the lithium salt monomer has a structure shown in a formula 1-1, and the polyoxyethylene ether monomer has a structure shown in a formula 1-3:
the invention adopts a multi-copolymerization mode to prepare the single-ion polymer electrolyte, can flexibly adjust the conditions of the species, the proportion and the like of the comonomer, realizes the design and the control of the polymer microstructure and obtains the polymer electrolyte with excellent performance.
Specifically, in some preferred embodiments, the above copolymerization process comprises: heating a mixed solution containing a lithium salt monomer, ethylene carbonate and a polyoxyethylene ether monomer to 50-70 ℃ under the inert gas atmosphere to obtain a pre-polymerized monomer solution; adding an initiator into the pre-polymerized monomer solution, and maintaining the temperature for polymerization reaction to obtain a polymerization product mixed solution; sequentially carrying out precipitation and solid-liquid separation on the mixed solution of the polymerization product, and sequentially washing and drying the obtained solid product to obtain an electrolyte; wherein the molar ratio of the lithium salt monomer to the ethylene carbonate to the polyoxyethylene ether monomer is 20-200: 20 to 500:10 to 100, and the polymerization reaction time is 12 to 72 hours.
In specific implementation, the lithium salt monomer, ethylene vinyl carbonate, and polyoxyethylene ether monomer may be dissolved in a solvent (denoted as a first solvent), then the obtained mixed solution is subjected to at least three vacuum-nitrogen charging processes to remove oxygen, and then the temperature of the removed mixed solution is raised to 50-70 ℃ to obtain a pre-polymerization monomer solution, where the temperature raising mode may be oil bath temperature raising, but is not limited thereto. Wherein, the molar ratio of the lithium salt monomer, the ethylene carbonate and the polyoxyethylene ether monomer can be adjusted according to the expected m, n and k values in the structure of the formula I; the polymerization temperature (i.e., the temperature after the temperature rise) may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or a range composed of any two of these values, and the polymerization time may be, for example, 12h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 72h or a range composed of any two of these values.
In the preparation process, the mixed solution of the polymerization product can be precipitated by adopting anhydrous ether, namely, the mixed solution of the polymerization product is added into the anhydrous ether for precipitation, then the obtained solid product is filtered, the obtained solid product is washed by adopting water so as to remove impurities such as unreacted monomers and the like possibly existing on the solid product, then the solid product is dried, the drying temperature can be 70-90 ℃, the drying time can be 10-20h, and in the specific implementation, the vacuum drying can be carried out in a vacuum oven.
In some embodiments, the process of adding the initiator to the pre-polymerized monomer solution may comprise: dissolving an initiator in a first solvent to obtain an initiator solution, and then dropwise adding the initiator solution into a prepolymerization monomer solution by using a constant-pressure dropping funnel; wherein the dropping time of the initiator solution is 0.5-10 h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or the range consisting of any two of the above values, and the adding amount of the initiator is controlled as follows: the mass of the initiator is 0.2 to 5% of the sum of the mass of the lithium salt monomer, the ethylene carbonate and the polyoxyethylene ether monomer, for example, 0.2%, 0.6%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or any two of these values.
Initiators conventional in the art may be employed in the present invention, for example, in some embodiments, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide t-butyl peroxide, methyl ethyl ketone peroxide.
In some embodiments, the first solvent may include at least one of N, N-dimethylformamide, tetrahydrofuran, dimethylsulfoxide, toluene.
The lithium salt monomer may be prepared by itself, and in some embodiments, the preparation process of the lithium salt monomer comprises:
(01) Dropwise adding thionyl chloride into a first mixed solution containing 2-acrylamide-2-lithium methylpropanesulfonate at 0-1 ℃ in an inert gas atmosphere to react for 1 +/-0.5 h, then transferring the mixture to a temperature of 25 +/-5 ℃ to react for 12 +/-2 h, sequentially carrying out precipitation and solid-liquid separation on the reacted first mixed solution, and sequentially washing and drying an obtained first solid product with ice water to obtain a product A;
(02) Adding the product A into a second mixed solution containing trifluoromethanesulfonamide and anhydrous triethylamine at 0-1 ℃ in an inert gas atmosphere, reacting for 1 +/-0.5 h, then transferring to 25 +/-5 ℃ for reacting for 12 +/-2 h, sequentially precipitating and carrying out solid-liquid separation on the reacted second mixed solution, and sequentially washing and drying the obtained second solid product with ice water to obtain a product B;
(03) And under the inert gas atmosphere, adding a lithium hydride solution into a third mixed solution formed by dissolving the product B in THF at 25 +/-5 ℃ to react for 12 +/-2 h, filtering the reacted third mixed solution, and washing and drying the obtained third solid product in sequence to obtain the lithium salt monomer with the structure shown in the formula 1-1.
In the step (01) and the step (02), dichloromethane may be used to precipitate the reacted mixed solution (the first mixed solution/the second mixed solution), that is, dichloromethane is added to the reacted mixed solution, the mixture is allowed to stand, so that solid matters in the mixture are precipitated, and then solid-liquid separation is achieved by filtration and the like, so as to obtain solid products (the first solid product/the second solid product). In the steps (01), (02) and (03), the drying temperature can be 70-90 ℃, and the drying time can be 10-15h.
In the step (01), 2-acrylamide-2-methylpropanesulfonic acid may be neutralized by using an alkaline lithium salt to obtain lithium 2-acrylamide-2-methylpropanesulfonate, and the lithium 2-acrylamide-2-methylpropanesulfonate is dissolved in a solvent (denoted as a second solvent) to obtain a first mixed solution; alternatively, the first mixed solution may be obtained by directly dissolving the basic lithium salt and 2-acrylamido-2-methylpropanesulfonic acid in the second solvent. Wherein the second solvent is Tetrahydrofuran (THF) and N, N-Dimethylformamide (DMF) according to the volume ratio of 10-15: 1, a mixed solvent; the basic lithium salt may include at least one of lithium carbonate and lithium hydroxide; the molar ratio of the lithium ions of the basic lithium salt to the lithium 2-acrylamido-2-methylpropanesulfonate is 1:1 +/-0.1, and in the specific operation, the basic lithium salt can be slightly excessive, for example, the molar ratio of the lithium ions of the basic lithium salt to the lithium 2-acrylamido-2-methylpropanesulfonate is 1 (1.05 to 1.1), so as to improve the conversion rate of the 2-acrylamido-2-methylpropanesulfonic acid and save the cost.
In the step (02), the trifluoromethanesulfonamide and the anhydrous triethylamine may be dissolved in THF to obtain a second mixed solution, and the process of adding the product a may include: and dissolving the product A in THF to obtain a product A solution, and then slowly dropwise adding the product A solution into the second mixed solution. In the step (02) and the step (03), lithium hydride may be dissolved in THF to form a lithium hydride solution, and in a specific operation, the lithium hydride solution may be slowly added dropwise to the second mixed solution/the third mixed solution. In the step (03), the third solid product may be washed with an organic solvent such as n-hexane.
In some embodiments, in the above preparation process, the molar ratio of lithium 2-acrylamido-2-methylpropanesulfonate, thionyl chloride, trifluoromethanesulfonamide, anhydrous triethylamine, and lithium hydride may be 1: 1. . + -. 0.1:1 ± 0.1:1 ± 0.1:1 + -0.1. Wherein, thionyl chloride and trifluoromethanesulfonamide may be slightly excessive, for example, the molar ratio of 2-acrylamide-2-methylpropanesulfonic acid lithium, thionyl chloride and trifluoromethanesulfonamide may be 1: (1.05-1.1): (1.05-1.1).
In the present invention, the inert gas atmosphere may be, for example, a nitrogen gas atmosphere and/or an argon gas atmosphere, but not limited thereto, and may be another suitable inert gas atmosphere.
In still another aspect of the present invention, there is provided an electrolyte membrane comprising a lithium salt and the above-described polyelectrolytes.
Specifically, in some embodiments, the ratio relationship between the multipolymer monoanionic polymer electrolyte and the lithium salt satisfies: the molar ratio of ethoxy groups in the multi-copolymerized mono-ionic polymer electrolyte to lithium elements (lithium ions) in the lithium salt is 3:1-50, for example, 3:1, 5:1, 10.
In some embodiments, the lithium salt includes at least one of lithium perchlorate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonate) imide, lithium tris (trifluoromethanesulfonate) methide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate, which can be better cooperated with the above-mentioned multi-copolymerized mono-ionic polymer electrolyte to further improve the ionic conductivity, electrochemical window and interface compatibility with electrodes of the electrolyte membrane.
In some embodiments, the thickness of the electrolyte membrane is 10 to 150 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or a range consisting of any two of these values, to facilitate the functioning of the electrolyte membrane.
The electrolyte membrane of the present invention is specifically a solid polymer electrolyte membrane, which may be prepared according to a conventional method in the art, and in some embodiments, may specifically include: mixing the multi-component copolymerized single-ion polymer electrolyte with lithium salt in a solvent (marked as a third solvent) to prepare a uniform film forming solution (generally in a slurry shape), casting the film forming solution in a mold, and drying to prepare the polymer electrolyte film. The mold may be a teflon mold, but not limited thereto, and may also be other suitable molds.
Specifically, in the preparation process of the electrolyte membrane, the drying temperature may be 50 to 120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or a range composed of any two of these values, and the drying time may be 12 to 72 hours, for example, 12 hours, 15 hours, 20 hours, 30 hours, 40h, 50 hours, 60 hours, 65 hours, 72 hours or a range composed of any two of these values. The third solvent may include at least one of N-methylpyrrolidone, N-dimethylformamide, acetonitrile, ethyl acetate, and dimethylsulfoxide.
In still another aspect of the present invention, there is provided a battery including the above electrolyte membrane.
Specifically, the battery further includes a positive electrode sheet and a negative electrode sheet, and the electrolyte separator is located between and spaces the positive electrode sheet and the negative electrode sheet as a solid electrolyte. The battery may include a lithium ion battery, which may be manufactured according to a conventional method in the art and will not be described in detail.
In still another aspect of the present invention, an electronic device is provided, which includes the above battery.
The implementation of the invention has at least the following beneficial effects:
according to the invention, the lithium salt monomer with a specific structure is adopted, and compared with the conventional polyanionic lithium salt, the lithium salt monomer has the advantages that the size of an anionic group formed in a single-ion polymer electrolyte is larger, the charge is more dispersed, the electronic delocalization effect is strong, the interaction of positive ions and negative ions is weaker, so that the transmission of ions (such as lithium ions) is smoother and more stable, and therefore, the electrolyte membrane of the invention has the characteristics of good ionic conductivity, ion migration coefficient and the like; meanwhile, the invention introduces side chain structures such as ethylene carbonate ethylene ester group of carbonate structure, polyoxyethylene ether group of specific structure and the like into the single ion polymer electrolyte, and the side chain type carbonate structure provides a wider electrochemical window, and can effectively reduce the crystallinity of the main chain, so that the electrolyte membrane has good adaptability to the volume change of the electrode; the polyoxyethylene ether group can effectively improve the flexibility of the single-ion conductor polymer electrolyte membrane, so that the polymer electrolyte membrane and electrodes have good interface compatibility; in addition, the polyoxyethylene ether side chain with both polarity and proper length is beneficial to the interaction between the macromolecular chain segments of the multipolymer, ensures the mechanical properties of the multipolymer single-ion conductor polymer electrolyte and the electrolyte membrane, and can also relieve the problems of lithium dendrite generation of the lithium ion Chi Yi and the like.
Drawings
FIG. 1 is a Fourier infrared spectrum (wave number on abscissa) of each monomer and electrolyte in example 1 of the present invention;
FIG. 2 shows NMR of the electrolyte in example 1 of the present invention 1 H spectrum (500 MHz) diagram;
FIG. 3 is a graph showing the impedance of the electrolyte membrane of example 1 of the invention at different temperatures;
fig. 4 is a graph showing electrochemical window test results (potential on the abscissa and Current on the ordinate) of the electrolyte membrane of example 1 of the present invention;
FIG. 5 is a graph showing impedance plots before (before) and after (after) polarization of the electrolyte membrane and a graph showing a change in current with Time (Time) during polarization according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
1. Synthesis of lithium salt monomer (1-1)
Dissolving 0.89g of lithium hydroxide and 4.14g of 2-acrylamide-2-methylpropanesulfonic acid in 20ml of a second solvent to obtain a first mixed solution; dropwise adding 2.40g of thionyl chloride into the first mixed solution at 0-1 ℃ in an argon atmosphere, reacting for 1h, then transferring to 25 ℃ for reacting for 12h, sequentially precipitating the first mixed solution after reaction (by adopting dichloromethane for precipitation) and carrying out solid-liquid separation, washing the obtained first solid product with ice water, and drying at 80 ℃ for 12h to obtain a product A; wherein the second solvent is a mixed solvent formed by THF and DMF according to a volume ratio of 10;
dissolving 5.62g of trifluoromethanesulfonamide and 2.02g of anhydrous triethylamine in 30ml of THF to obtain a uniform second mixed solution; dissolving the product A in 10ml of THF to obtain a uniform product A solution; slowly dropwise adding the product A solution into the second mixed solution at 0-1 ℃ under the argon atmosphere, reacting for 1h, then transferring to 25 ℃ for reacting for 12h, sequentially carrying out precipitation (adopting dichloromethane for precipitation) and solid-liquid separation on the reacted second mixed solution, washing the obtained second solid product with ice water, and drying at 80 ℃ for 12h to obtain a product B;
0.16g of lithium hydride was dissolved in 10ml of THF to obtain a uniform lithium hydride solution; dissolving the product B in 20ml of THF to obtain a uniform third mixed solution; slowly and dropwise adding a lithium hydride solution into the third mixed solution at 25 ℃ in an argon atmosphere, reacting for 12 hours, filtering the reacted third mixed solution, washing the obtained third solid product with n-hexane, and drying at 80 ℃ for 12 hours to obtain a lithium salt monomer, wherein the structure of the lithium salt monomer is 1-1.
2. Synthesis of Polycopolymerized Mono-Ionic Polymer electrolyte (formula Ia)
Dissolving 3.60g of lithium salt monomer (1-1), 1.14g of ethylene carbonate (1-2) and 2.38g of polyoxyethylene ether (1-3) in 20ml of DMF solvent, repeatedly carrying out three times of vacuum pumping-nitrogen filling processes for deoxygenation under the stirring state, and then heating the deoxygenated mixed system in an oil bath to 65 ℃ to form a pre-polymerization monomer solution;
15mg of Azobisisobutyronitrile (AIBN) was dissolved in 10ml of DMF solvent to obtain an initiator solution; slowly dripping an initiator solution into a pre-polymerized monomer solution through a constant-pressure dropping funnel in a nitrogen atmosphere, and then carrying out polymerization reaction at a constant temperature of 65 ℃ to obtain a polymerization product mixed solution; wherein the dripping time of the initiator solution is controlled to be 1h, and the polymerization reaction time is 24h;
precipitating the mixed solution of the polymerization products by adopting anhydrous ether, then filtering, washing the obtained solid product with deionized water for three times, placing the solid product in a vacuum oven, and drying the solid product for 12 hours at the temperature of 80 ℃ to obtain the electrolyte of the multi-copolymerization single ion polymer;
the infrared spectrum of the electrolyte is shown in figure 1 after testing, and nuclear magnetic resonance 1 The spectrum H is shown in FIG. 2, and the structure is shown in the following formula Ia.
The reaction formula in the synthesis process is as follows:
3. preparation of electrolyte Membrane
Dissolving 1.5g of multi-component copolymerized mono-ion polymer electrolyte (formula Ia) in 10ml of acetonitrile solvent, adding lithium bis (trifluoromethyl) sulfonyl imide, and uniformly stirring to obtain a slurry-shaped film forming solution; casting the film-forming solution in a polytetrafluoroethylene mold, and then placing the polytetrafluoroethylene mold in a vacuum oven at 60 ℃ for drying for 12 hours to obtain a solid polymer electrolyte film with the thickness of 45 mu m; wherein the adding amount of the lithium bis (trifluoromethyl) sulfonyl imide meets the following requirements: the molar ratio of ethoxy groups in the polyelectrolytes to lithium ions in the lithium salt was 4:1.
4. Electrolyte membrane performance test results
The results of the impedance test of the above electrolyte membrane are shown in fig. 3, and it can be seen that the electrolyte membrane has good ionic conductivity, particularly superior ionic conductivity at 60 c, and the lithium ion conductivity at 60 c is calculated to be 2.89 x 10 -4 S/cm。
The electrochemical window test results of the electrolyte membrane are shown in fig. 4, and it can be seen that the electrolyte membrane has a withstand voltage value as high as 5.0V and has a wide electrochemical window.
The impedance test results before and after the electrolyte membrane is polarized are shown in figure 5, and the lithium ion migration number of the electrolyte membrane is calculated to be as high as 0.58, so that the electrolyte membrane shows a high ion migration coefficient.
In addition, the electrolyte membrane also exhibits good flexibility, and has good interfacial compatibility with electrodes.
Claims (10)
1. A multi-copolymerized mono-ionic polymer electrolyte, characterized in that it has the structure shown in formula I:
wherein m is an integer of 20 to 200, n is an integer of 20 to 500, k is an integer of 10 to 100, and i is 8 or 9.
2. The method for preparing the electrolyte according to claim 1, comprising: copolymerizing a lithium salt monomer, ethylene carbonate and a polyoxyethylene ether monomer to obtain the electrolyte; the lithium salt monomer has a structure shown in a formula 1-1, and the polyoxyethylene ether monomer has a structure shown in a formula 1-3:
3. the method of claim 2, wherein the copolymerization process comprises: heating a mixed solution containing a lithium salt monomer, ethylene carbonate and a polyoxyethylene ether monomer to 50-70 ℃ under an inert gas atmosphere to obtain a pre-polymerization monomer solution; adding an initiator into the pre-polymerization monomer solution, and maintaining the temperature for polymerization reaction to obtain a polymerization product mixed solution; sequentially carrying out precipitation and solid-liquid separation on the mixed solution of the polymerization products, and sequentially washing and drying the obtained solid products to obtain electrolyte; wherein the molar ratio of the lithium salt monomer to the ethylene carbonate to the polyoxyethylene ether monomer is 20-200: 20 to 500:10 to 100, and the polymerization reaction time is 12 to 72 hours.
4. The method of claim 3, wherein the adding of the initiator to the pre-polymerized monomer solution comprises: dissolving an initiator in a solvent to obtain an initiator solution, and then dropwise adding the initiator solution into the prepolymerization monomer solution by adopting a constant-pressure dropping funnel; wherein the dropping time of the initiator solution is 0.5-10 h, and the adding amount of the initiator is controlled as follows: the mass of the initiator is 0.2-5% of the sum of the mass of the lithium salt monomer, the ethylene carbonate and the polyoxyethylene ether monomer.
5. An electrolyte membrane comprising a lithium salt and the multipolymer monoionic polymer electrolyte of claim 1.
6. The electrolyte membrane according to claim 5, wherein a proportional relationship between the multiple copolymerized single-ion polymer electrolyte and the lithium salt satisfies: the molar ratio of the ethoxy groups in the multi-copolymerized single-ion polymer electrolyte to the lithium elements in the lithium salt is 3:1-50.
7. The electrolyte membrane according to claim 5 or 6, wherein the lithium salt comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonic) imide, lithium tris (trifluoromethanesulfonic) methide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate.
8. The electrolyte membrane according to claim 5 or 6, wherein the thickness of the electrolyte membrane is 10 to 150 μm.
9. A battery comprising the electrolyte membrane according to any one of claims 5 to 8.
10. An electronic device comprising the battery of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110188835.4A CN112979873B (en) | 2021-02-19 | 2021-02-19 | Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110188835.4A CN112979873B (en) | 2021-02-19 | 2021-02-19 | Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112979873A CN112979873A (en) | 2021-06-18 |
| CN112979873B true CN112979873B (en) | 2022-11-22 |
Family
ID=76393454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110188835.4A Active CN112979873B (en) | 2021-02-19 | 2021-02-19 | Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112979873B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117497842B (en) * | 2023-12-27 | 2024-03-12 | 江苏蓝固新能源科技有限公司 | Polymer electrolyte, preparation method and application thereof in secondary battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000082494A (en) * | 1998-09-03 | 2000-03-21 | Sanyo Chem Ind Ltd | Flame-resistant nonaqueous electrolyte and secondary battery using the same |
| CN105914397A (en) * | 2016-06-28 | 2016-08-31 | 哈尔滨工业大学 | Fluorine-containing polymer electrolytes and preparation methods and applications thereof |
| WO2018059484A1 (en) * | 2016-09-29 | 2018-04-05 | 比亚迪股份有限公司 | Anionic ionic liquid polymer, preparation method therefor and application thereof |
| CN108808082A (en) * | 2018-08-15 | 2018-11-13 | 中南大学 | A kind of solid polyelectrolyte and preparation method for lithium ion battery |
| CN110003399A (en) * | 2019-03-06 | 2019-07-12 | 南开大学 | A kind of preparation and application of single ion conductive polymer electrolyte film |
| KR102188558B1 (en) * | 2019-09-06 | 2020-12-08 | 건국대학교 글로컬산학협력단 | PEALiFSI polymer compound, process for preparing the same and use as solid electrolyte thereof |
| CN112239519A (en) * | 2020-09-30 | 2021-01-19 | 氟金(上海)新材料有限公司 | Lithium carbonate-containing ionic copolymer and preparation method thereof |
-
2021
- 2021-02-19 CN CN202110188835.4A patent/CN112979873B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000082494A (en) * | 1998-09-03 | 2000-03-21 | Sanyo Chem Ind Ltd | Flame-resistant nonaqueous electrolyte and secondary battery using the same |
| CN105914397A (en) * | 2016-06-28 | 2016-08-31 | 哈尔滨工业大学 | Fluorine-containing polymer electrolytes and preparation methods and applications thereof |
| WO2018059484A1 (en) * | 2016-09-29 | 2018-04-05 | 比亚迪股份有限公司 | Anionic ionic liquid polymer, preparation method therefor and application thereof |
| CN108808082A (en) * | 2018-08-15 | 2018-11-13 | 中南大学 | A kind of solid polyelectrolyte and preparation method for lithium ion battery |
| CN110003399A (en) * | 2019-03-06 | 2019-07-12 | 南开大学 | A kind of preparation and application of single ion conductive polymer electrolyte film |
| KR102188558B1 (en) * | 2019-09-06 | 2020-12-08 | 건국대학교 글로컬산학협력단 | PEALiFSI polymer compound, process for preparing the same and use as solid electrolyte thereof |
| CN112239519A (en) * | 2020-09-30 | 2021-01-19 | 氟金(上海)新材料有限公司 | Lithium carbonate-containing ionic copolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112979873A (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4741140B2 (en) | POLYMER ELECTROLYTE, BATTERY CELL CONTAINING POLYMER ELECTROLYTE, AND METHOD FOR PRODUCING POLYMER ELECTROLYTE | |
| CN111732724B (en) | Polyaryletherketone single-ion polymer and single-ion gel polymer electrolyte | |
| CN111533864B (en) | Block copolymer and preparation method thereof, and all-solid-state copolymer electrolyte membrane and preparation method thereof | |
| CN106887622A (en) | Fluorine-containing single ion conductor polymer dielectric and preparation method and application | |
| CN112979873B (en) | Multi-copolymerized single ion polymer electrolyte and preparation method and application thereof | |
| US20170263936A1 (en) | Lithium metal electrode, method for preparing the same, and lithium rechargeable battery using the same | |
| CN112159507A (en) | Solid electrolyte based on four-arm polyoxyethylene-polymeric ionic liquid block copolymer and preparation method thereof | |
| CN108341964B (en) | Functional polymer, polymer electrolyte for lithium battery, preparation method of polymer electrolyte, polymer electrolyte membrane and lithium ion battery | |
| CN111987354A (en) | PEO side chain segment-containing solid lithium battery polymer electrolyte and preparation method thereof | |
| CN111224184A (en) | Preparation method and application of solid electrolyte interface additive of lithium ion battery | |
| CN113707935B (en) | Polyfluorinated polymer solid electrolyte material and preparation method thereof | |
| CN113178561B (en) | Negative electrode material modified by reactive two-dimensional molecular brush SEI film, and preparation method and application thereof | |
| CN112993396B (en) | Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery | |
| CN112701418B (en) | Lithium battery diaphragm with overcharge protection function and preparation method thereof | |
| CN112481829A (en) | Single-ion conductor polymer electrolyte composite diaphragm, and preparation method and application thereof | |
| CN113540559B (en) | ZIF-8@ PEGMEM-co-AMPS-Li single ion polymer solid electrolyte and preparation method thereof | |
| CN111987351A (en) | Polymer gel electrolyte and preparation method and application thereof | |
| CN114447417B (en) | Modified inorganic fast ion conductor and preparation method and application thereof | |
| CN114229858B (en) | Energy storage electrode material Ba 6 Nb 14 Si 4 O 47 Preparation method and application of (C) | |
| CN111825874B (en) | Polymer electrolyte prepared based on surface initiation, preparation and application thereof | |
| CN117487483B (en) | Ionic polymer binder and preparation method and application thereof | |
| CN114006028B (en) | Modified inorganic fast ion conductor and preparation method and application thereof | |
| CN116190779A (en) | Polymer electrolyte membrane, preparation method thereof and lithium ion battery | |
| TW202313743A (en) | Copolymer electrolyte, preparation method thereof and solid-state lithium secondary batteries | |
| CN116799297A (en) | Organic solid electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |