CN114702626B - Nitrile polymer electrolyte matrix material, electrolyte and battery - Google Patents
Nitrile polymer electrolyte matrix material, electrolyte and battery Download PDFInfo
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- CN114702626B CN114702626B CN202210318555.5A CN202210318555A CN114702626B CN 114702626 B CN114702626 B CN 114702626B CN 202210318555 A CN202210318555 A CN 202210318555A CN 114702626 B CN114702626 B CN 114702626B
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a nitrile polymer electrolyte matrix material, an electrolyte and a battery, belonging to the technical field of polymer electrolyte materials of energy storage devices such as solid-state lithium batteries and the like. The invention solves the technical problem of providing a nitrile polymer electrolyte matrix material. The matrix material is formed by free radical polymerization of acrylonitrile-acrylic acid copolymer, sulfonate organic monomer with double bond and reaction monomer, wherein the reaction monomer comprises N, N-diethyl cyanoacrylamide (BCEAM). The electrolyte membrane impregnated with the organic electrolyte solution is suitable for a dimethyl carbonate and diethyl carbonate electrolyte system, and has a liquid absorption rate of less than 250% and an ionic conductivity of 10% ‑4 ～10 ‑3 Scm ‑1 And has good mechanical strength, and can be used as polymer electrolyte to replace liquid electrolyte so as to improve the safety performance of the lithium ion battery. The material has low cost, simple preparation method, environment protection by taking water as a medium, no need of special equipment and contribution to industrial production.
Description
Technical Field
The invention relates to a nitrile polymer electrolyte matrix material, an electrolyte and a battery, belonging to the technical field of polymer electrolyte materials of energy storage devices such as solid-state lithium batteries and the like.
Background
The solid-state lithium battery is an ultimate goal of the development of the power battery of the new energy automobile, and the application of the solid-state lithium battery to the new energy automobile can improve the safety and the service life of the solid-state lithium battery. The core technology of solid-state lithium batteries is to replace liquid electrolytes with solid electrolytes. The primary task of developing solid-state lithium batteries is to develop solid-state electrolytes with high performance, low cost and wide application process universality.
All solid state electrolytes have been developed in three technical routes, sulfide, oxide and polymer electrolytes, respectively. The sulfide and oxide solid electrolyte has the advantages of excellent ionic conductivity, stable electrical performance and the like, but the solid battery manufacturing process is difficult to be compatible with the existing lithium battery manufacturing process, a stove is needed to be replaced, and the solid battery manufacturing process and the solid battery manufacturing flow are redesigned and established, so that high production cost is caused. The polymer electrolyte is prepared by dissolving lithium salt in a polymer solution, and volatilizing the solvent by adopting a film coating technology. The polymer electrolyte membrane is completely compatible with the existing lithium battery manufacturing process, has good process universality, and the polymer electrolyte is used for manufacturing the solid-state battery, so that the polymer electrolyte membrane is a production process which is easy to process and low in cost. The current classification of polymer electrolytes is mainly of the following two types: the pure solid polymer electrolyte and the gel polymer electrolyte have the characteristics of higher mechanical strength, excellent battery easy processing property and safety, long service life and the like, so that the pure solid polymer electrolyte is an ideal solid electrolyte. However, the polymer solid electrolyte has low ionic conductivity at room temperature, and has no commercial application value at present. The gel polymer electrolyte is usually prepared by using polymer with solubility parameter similar to that of organic solvent of electrolyte as matrix at concentration of 1.0mol.L -1 The electrolyte is obtained by impregnating and swelling the polymer matrix. The ionic conductivity of the gel polymer electrolyte increases with increasing content of the electrolyte solution contained, and at higher electrolyte solution contents, the conductivity can approach that of the liquid electrolyte. Although the gel polymer electrolyte with high electrolyte solution content is helpful for improving the battery performance, the mechanical strength of the gel polymer electrolyte is reduced, the safety performance of the battery is not improved, and the original purpose of improving the safety of the lithium battery by the gel polymer electrolyte is eliminated. Ionic conductivity and mechanical property of gel polymer electrolyteThis conflict that can exist is an important issue in the development of gel polymer electrolytes.
Typically, the ionic conductivity of a polymer electrolyte is related to the number of free ions per unit volume, and a polymer electrolyte can achieve higher ionic conductivity only at higher free ion concentrations per unit volume. The absorption of the electrolyte is 300-500% of the weight of the polymer matrix, and the solvent of the electrolyte is also good solvent of the polymer matrix and is mutually soluble, so that the cohesive energy of the polymer matrix is reduced under the action of the good solvent, and the mechanical strength of the polymer electrolyte is rapidly reduced and the mechanical property is deteriorated. Therefore, there is a need to solve the problem of the ionic conductivity and mechanical properties of gel polymer electrolytes.
In addition, the existing gel polymer electrolyte mainly adopts polyvinyl alcohol as a main substrate, the polyvinyl alcohol belongs to a strong polar polymer, the polyvinyl alcohol is not compatible with most low-polarity ester solvents, the prepared polymer electrolyte is only suitable for electrolyte systems formed by strong polar solvents such as propylene carbonate, ethylene carbonate and the like, and is not suitable for electrolyte systems formed by low-polarity solvents such as dimethyl carbonate, diethyl carbonate and the like. In order to adapt to the existing lithium ion battery production system and process, it is necessary to develop a polymer electrolyte material suitable for the electrolyte system of dimethyl carbonate and diethyl carbonate.
Disclosure of Invention
The invention solves the technical problem of providing a nitrile polymer electrolyte matrix material suitable for a dimethyl carbonate and diethyl carbonate electrolyte system.
The nitrile polymer electrolyte matrix material is formed by free radical polymerization of acrylonitrile-acrylic acid copolymer, sulfonate organic monomer with double bond and reaction monomer, wherein the reaction monomer comprises N, N-diethyl cyanoacrylamide (BCEAM).
In one embodiment of the present invention, the sulfonate organic monomer having a double bond is 5.0 to 20% by weight of N, N-diethyl cyanoacrylamide; the weight of the reaction monomer is 50-300% of the weight of the acrylonitrile-acrylic acid copolymer.
In one embodiment of the invention, the sulfonate organic monomer having a double bond is present in an amount of 14.0 to 20% by weight based on the weight of N, N-diethylcyanoacrylamide.
In one embodiment of the invention, the weight of the reactive monomer is 80 to 170% of the weight of the acrylonitrile-acrylic acid copolymer.
In a specific embodiment, the sulfonate organic monomer having a double bond includes at least one of sodium vinylsulfonate, sodium allylsulfonate, sodium methallylsulfonate, 2-acrylamide-2-methylpropanesulfonic acid, sodium p-styrenesulfonate.
In one embodiment, the acrylonitrile-acrylic acid copolymer is polymerized from acrylonitrile monomers including at least one of acrylonitrile, methacrylonitrile, and N, N-diethyl cyanoacrylamide monomers and acrylic monomers including at least one of acrylic acid and methacrylic acid.
In a preferred embodiment of the invention, the weight ratio of acrylic monomer to acrylonitrile monomer is 25 to 40% to 60 to 80%. In one embodiment, the weight ratio of acrylic monomer to acrylonitrile monomer is 30-40% to 60-70%.
Specifically, the acrylonitrile-acrylic acid copolymer is prepared by the following method: mixing water and acrylic monomers, regulating the pH to 7-9, heating to 50-70 ℃, adding an initiator, and beginning to dropwise add acrylonitrile monomers for polymerization reaction for 8-24 hr to obtain the acrylic polymer.
In a specific embodiment, the reaction monomer further comprises an acrylic monomer, and the weight ratio of the N, N-diethyl cyanoacrylamide to the acrylic monomer is 60-90 percent, 10-40 percent.
The acrylic monomer may be one commonly used in the art. The invention is provided withIn an embodiment of the body, the acrylic monomer has a chemical formula of CH 2 ＝CR 1 COOR 2 At least one of (1), wherein R 1 is-H or-CH 3 ，R 2 Is- (CH) 2 ) n CH 3 N is an integer of 0 to 12.
The invention also provides a nitrile polymer electrolyte.
The nitrile polymer electrolyte comprises a polymer matrix and electrolyte salt, wherein the polymer matrix is the nitrile polymer electrolyte matrix material.
The electrolyte salt may be an electrolyte salt commonly used in the present invention, such as a lithium salt. In one embodiment of the invention, the electrolyte salt is LiTFSI (lithium bistrifluoro-methane-sulfonate imide), LIFSI (lithium bistrifluoro-sulfonate imide), liPF 6 Lithium hexafluorophosphate, liBF 4 Lithium tetrafluoroborate, liBOB (lithium oxalato borate), liDFOB (lithium oxalato difluoroborate), liPF 2 O 2 (lithium difluorophosphate) and the like.
The nitrile polymer electrolyte is prepared by a conventional method. In one embodiment of the invention, the gel polymer electrolyte matrix material is cast into a film, then immersed in electrolyte, and immersed for 24 hours at 70 ℃ to obtain the gel polymer electrolyte matrix material. The electrolyte is a conventional electrolyte in the art including, but not limited to, an electrolyte in a dimethyl carbonate or diethyl carbonate system.
The invention also provides a gel polymer battery.
The gel polymer battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the gel polymer electrolyte.
The gel polymer battery can be a lithium storage battery, and the common positive electrode and the common negative electrode of the lithium battery are suitable for the invention.
Compared with the prior art, the invention has the following beneficial effects:
the production process of the nitrile polymer electrolyte matrix material of the invention uses water as medium, and has no pollution and harm to the health of the environment and operation production personnelIs a green and environment-friendly production technology. The matrix material can be cast into a film by a common method, and the obtained film is impregnated with an organic electrolyte solution to obtain a polymer electrolyte film which is applicable to electrolyte systems of dimethyl carbonate and diethyl carbonate, and has the liquid absorption rate of less than 250 percent and the ionic conductivity of 10 percent -4 ～10 -3 Scm -1 And has good mechanical strength, and can be used as polymer electrolyte to replace liquid electrolyte so as to improve the safety performance of the lithium ion battery.
The nitrile polymer electrolyte matrix material has the advantages of lower raw material cost, simple preparation method, no need of special equipment, lower cost and contribution to industrial production.
Detailed Description
The technical approach for solving the contradiction between the ionic conductivity and the mechanical property of the polymer electrolyte is as follows: the primary importance is to increase the number of dissociable ion sources that the polymer matrix itself should contain; secondly, the polymer matrix should contain a component which can complex or chelate metal ions, and the metal complex or chelate is favorable for generating free ions under the action of a solvent; the polymer matrix should be a strong polar polymer, and is compatible with and incompatible with the solvent, so as to avoid the great reduction of the mechanical properties of the material caused by the action of the solvent.
Based on the technical approach for solving the mechanical property of the polymer electrolyte, the invention provides the nitrile polymer electrolyte matrix material which can show higher ionic conductivity by absorbing a small amount of organic electrolyte, has good mechanical strength, and can be suitable for electrolyte systems of dimethyl carbonate and diethyl carbonate.
The nitrile polymer electrolyte matrix material is formed by free radical polymerization of acrylonitrile-acrylic acid copolymer, sulfonate organic monomer with double bond and reaction monomer, wherein the reaction monomer comprises N, N-diethyl cyanoacrylamide (BCEAM).
The nitrile polymer electrolyte matrix material of the invention can be cast into a film by a common method, and the obtained film is impregnated with an organic electrolyte solution to obtain a polymer electrolyte film, wherein the polymer electrolyte film is prepared by the methodThe electrolyte membrane is suitable for a dimethyl carbonate and diethyl carbonate electrolyte system, the liquid absorption rate is less than 250%, and the ionic conductivity is 10 -4 ～10 -3 Scm -1 And has good mechanical strength, and can be used as polymer electrolyte to replace liquid electrolyte so as to improve the safety performance of the lithium ion battery.
Wherein, the structural formula of the N, N-diethyl cyanoacrylamide (abbreviated as BCEAM) is as follows:
BCEAM may be prepared by methods commonly used in the art, and in one embodiment, BCEAM is synthesized from acrylamide and acrylonitrile using a Michael addition reaction. The beneficial effect of introducing BCEAM in the invention is that nitrile groups of the BCEAM monomer have non-bonded lone pair electrons, the nitrile groups have stronger coordination capacity to metal ions to form a complex, and the nitrile groups and the metal ion complex have ion conductivity, thus being very beneficial to improving the conductivity of polymer electrolyte.
In one embodiment of the present invention, the sulfonate organic monomer having a double bond is 5.0 to 20% by weight of N, N-diethyl cyanoacrylamide; the weight of the reaction monomer is 50-300% of the weight of the acrylonitrile-acrylic acid copolymer.
In one embodiment of the invention, the sulfonate organic monomer having a double bond is present in an amount of 14 to 20% by weight of N, N-diethylcyanoacrylamide.
In one embodiment of the invention, the weight of the reactive monomer is 80 to 170% of the weight of the acrylonitrile-acrylic acid copolymer.
Sulfonate organic monomers having double bonds commonly used in the art are suitable for use in the present invention. In a specific embodiment, the sulfonate organic monomer having a double bond includes at least one of Sodium Vinyl Sulfonate (SVS), sodium Allyl Sulfonate (SAS), sodium methacrylate sulfonate (SMAS), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), sodium p-styrene sulfonate (SSS).
The acrylonitrile-acrylic acid copolymer is an acrylonitrile-acrylic acid copolymer commonly used in the art. In one embodiment, the acrylonitrile-acrylic acid copolymer is polymerized from acrylonitrile monomers including at least one of Acrylonitrile (AN), methacrylonitrile (MAN), and N, N-diethyl cyanoacrylamide (BCEAM) monomers and acrylic monomers including at least one of Acrylic Acid (AA) and methacrylic acid (MAA).
In a preferred embodiment of the invention, the weight ratio of acrylic monomer to acrylonitrile monomer is 25 to 40% to 60 to 80%. When the acrylic monomer content is less than 25%, the copolymer tends to settle and an aqueous acrylonitrile-acrylic acid copolymer solution cannot be formed. In one embodiment, the weight ratio of acrylic monomer to acrylonitrile monomer is 30-40% to 60-70%.
In a specific embodiment of the invention, the weight ratio of acrylic monomer to acrylonitrile monomer is 35% to 65%.
Specifically, the acrylonitrile-acrylic acid copolymer is prepared by the following method: mixing water and acrylic monomers, regulating the pH to 7-9, heating to 50-70 ℃, adding an initiator, and beginning to dropwise add acrylonitrile monomers for polymerization reaction for 8-24 hr to obtain the acrylic polymer.
In a specific embodiment, lithium hydroxide is added to adjust the pH. The pH value is adjusted by lithium hydroxide, and other atoms can not be introduced into the lithium ion battery.
In a specific embodiment, the reaction monomer further comprises an acrylic monomer, and the weight ratio of the N, N-diethyl cyanoacrylamide to the acrylic monomer is 60-90 percent, 10-40 percent. The absorption amount of the electrolyte solution of the polymer electrolyte membrane and the flexibility of the polymer electrolyte membrane can be regulated by adding the ester monomer into the polymer.
The acrylic monomer may be one commonly used in the art. In a specific embodiment of the invention, the acrylic monomer has a chemical formula of CH 2 ＝CR 1 COOR 2 At least one of, itR in (B) 1 is-H or-CH 3 ，R 2 Is- (CH) 2 ) n CH 3 N is an integer of 0 to 12.
In some specific embodiments, the acrylic monomers include, but are not limited to, at least one of Methyl Acrylate (MA), ethyl Acrylate (EA), propyl Acrylate (PA), butyl Acrylate (BA), vinyl Acetate (VAC), isooctyl acrylate (EHA).
The nitrile polymer electrolyte matrix material can be obtained by adopting a common polymerization method. In one embodiment, the method comprises the following steps:
firstly, deionized water and acrylic monomers are added into a glass reaction bottle provided with a stirring, heating and condensing device, lithium hydroxide (LiOH) is used for neutralizing the reaction liquid to pH 7-9, then a free radical initiator is added at a certain temperature, and acrylonitrile monomers are added dropwise for polymerization reaction; then adding N, N-diethyl cyanoacrylamide (BCEAM) monomer and sulfonate organic monomer into the water solution of the reacted acrylonitrile and lithium acrylate copolymer to carry out secondary free radical initiation polymerization, thereby obtaining BCEAM polymerization emulsion; or adding one or more acrylic monomers for copolymerization to obtain the poly BCEAM-acrylic monomer copolymerization emulsion.
In a preferred embodiment, the synthesized BCEAM polymerization emulsion or BCEAM-acrylic ester copolymerization emulsion is cast into a film, the film is dried, the moisture is dried, and the film is heated and dried in vacuum to obtain a polymer electrolyte matrix material film, and then the film is impregnated with electrolyte to obtain the film with the liquid absorption of less than 250 percent and the ionic conductivity of 10 -4 ～10 -3 Scm -1 And has good mechanical strength.
Specifically, the preparation method comprises the following steps:
1. the preparation method of the acrylic acid and acrylonitrile copolymer aqueous solution comprises the following steps: firstly adding deionized water and acrylic monomers into a glass reaction bottle provided with a stirring, heating and condensing device, neutralizing the reaction liquid to pH 7-9 by using lithium hydroxide (LiOH), then heating to 50-70 ℃, adding ammonium persulfate, starting to dropwise add acrylonitrile monomers for polymerization reaction, and obtaining acrylic and acrylonitrile copolymer aqueous solution after 8-24 hr, wherein the acrylic monomers and acrylonitrile monomers in the copolymer respectively comprise 25-40% and 60-75%, and the solid content of the copolymer aqueous solution is 10-20%.
A preparation method of BCEAM polymerization emulsion or BCEAM-acrylic ester polymerization emulsion: and (3) adding organic sulfonate monomer and BCEAM monomer or simultaneously adding BCEAM and acrylic ester monomer into the aqueous solution of the copolymer synthesized in the step (1) according to the metering, stirring and mixing, adjusting the reaction temperature to 60-85 ℃, and then adding ammonium persulfate to initiate polymerization for 4-12 hours. The content of the sulfonate organic monomer is 5.0-20% of the mass of the BCEAM, the addition of the BCEAM or the acrylic ester is 100-300% of the solid mass of the acrylic acid and acrylonitrile copolymer, wherein the mixing ratio of the BCEAM and the acrylic ester monomer is 60-90%: 10-40%. The solid content of the BCEAM polymerization emulsion or the BCEAM-acrylic ester polymerization emulsion is 20-30 percent.
3. Pouring part of prepared BCEAM or BCEAM-acrylic ester polymerization emulsion into a plastic vessel, firstly drying water in a blowing oven at 80-90 ℃, and then transferring the dried water into a vacuum oven to be dried in vacuum at 85-90 ℃ for 24 hours. The sample after vacuum drying is stored in a glass desiccator for standby.
The invention also provides a nitrile polymer electrolyte.
The nitrile polymer electrolyte comprises a polymer matrix and electrolyte salt, wherein the polymer matrix is the nitrile polymer electrolyte matrix material.
The electrolyte salt may be an electrolyte salt commonly used in the present invention, such as a lithium salt. In one embodiment of the invention, the electrolyte salt is LiTFSI (lithium bistrifluoro-methane-sulfonate imide), LIFSI (lithium bistrifluoro-sulfonate imide), liPF 6 Lithium hexafluorophosphate, liBF 4 Lithium tetrafluoroborate, liBOB (lithium oxalato borate), liDFOB (lithium oxalato difluoroborate), liPF 2 O 2 (lithium difluorophosphate) and the like.
The nitrile polymer electrolyte is prepared by a conventional method. In one embodiment of the invention, the gel polymer electrolyte matrix material is cast into a film, then immersed in electrolyte, and immersed for 24 hours at 70 ℃ to obtain the gel polymer electrolyte matrix material. The electrolyte is a conventional electrolyte in the art including, but not limited to, an electrolyte in a dimethyl carbonate or diethyl carbonate system.
The invention also provides a gel polymer battery.
The gel polymer battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the gel polymer electrolyte.
The gel polymer battery can be a lithium storage battery, and the common positive electrode and the common negative electrode of the lithium battery are suitable for the invention.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
The preparation method of the dioxane solution of the BCEAM in the embodiment comprises the following steps:
700g of dioxane, 432g of acrylamide and 2g of sodium hydroxide are added into a glass reaction bottle provided with a stirring, heating and condensing device, the temperature is raised to 40 ℃, 640g of acrylonitrile is dripped after the temperature is constant, the dripping time is 7 hours, the reaction temperature is controlled within the range of 45+/-5 ℃, the constant temperature 45 ℃ is continued to react for 16 hours after the acrylonitrile dripping is finished, and finally the BCEAM dioxane solution with the concentration of about 60% is obtained, and the obtained BCEAM dioxane solution is yellow sticky.
Example 1
Adding 35g of AA monomer and 540g of deionized water into a glass reaction bottle provided with a stirring, heating and condensing device, adding 21g of LiOH to neutralize AA under stirring, introducing nitrogen to remove oxygen for 0.5 hour, heating to 60 ℃, adding 4g of 10% ammonium persulfate aqueous solution, simultaneously starting to dropwise add 65g of AN monomer, dropwise adding the monomer for about 3-5 hours, and then keeping the temperature for continuous reaction for 5 hours.
Adding 12g of AMPS and 140g of dioxane solution with 60% of BCEAM concentration into the synthesized AA-AN copolymer aqueous solution, adding 10g of 10% ammonium persulfate aqueous solution and 150g of deionized water, and raising the temperature to 70-75 ℃ for reaction for 4-6 hours to obtain the polymer copolymerization emulsion with the solid content of about 20%.
10g of the copolymer emulsion was weighed and poured into a plastic vessel, the water was first dried in a blowing oven at 80 to 90℃and then transferred into a vacuum oven to be dried at 85 to 90℃for 24 hours, then a sample having a thickness of about 0.5mm was immersed into an electrolyte for a conventional lithium ion battery, and the liquid absorption and the electrical conductivity of the polymer electrolyte membrane were measured after immersing at 70℃for 24 hours by the electrolyte, as shown in Table 1.
Wherein, the liquid absorption rate of the electrolyte solution of the polymer electrolyte membrane is measured:
the sample after vacuum drying is weighed and then immersed in ethylene carbonate/diethyl carbonate/dimethyl carbonate and LiPF 6 The electrolyte solution used in the conventional lithium ion battery is soaked at 70 ℃ for 24 hours and then taken out for weighing. Sample liquid absorption rate:
liquid absorption% = (weight after soaking-weight before soaking)/weight before soaking x100%.
Conductivity measurement of polymer electrolyte membrane:
the polymer electrolyte membrane having absorbed the electrolyte was tested for ionic conductivity using an electrochemical impedance meter.
Example 2
Adding 35g of AA monomer and 540g of deionized water into a glass reaction bottle provided with a stirring, heating and condensing device, adding 21g of LiOH to neutralize AA under stirring, introducing nitrogen to remove oxygen for 0.5 hour, heating to 60 ℃, adding 4g of 10% ammonium persulfate aqueous solution, simultaneously starting to dropwise add 65g of AN monomer, dropwise adding the monomer for about 3-5 hours, and then keeping the temperature for continuous reaction for 5 hours.
24g of AMPS and 280g of dioxane solution with 60% of BCEAM concentration are added into the synthesized AA-AN copolymer aqueous solution, 20g of 10% ammonium persulfate aqueous solution and 180g of deionized water are added, and the temperature is raised to 70-75 ℃ for reaction for 4-6 hours, so that the polymer copolymer emulsion with the solid content of about 25% is obtained.
10g of the copolymer emulsion was weighed and poured into a plastic vessel, the water was first dried in a blowing oven at 80 to 90℃and then transferred into a vacuum oven to be dried at 85 to 90℃for 24 hours, then a sample having a thickness of about 0.5mm was immersed into an electrolyte for a conventional lithium ion battery, and the liquid absorption and the electrical conductivity of the polymer electrolyte membrane were measured after immersing at 70℃for 24 hours by the electrolyte, as shown in Table 1.
Example 3
The polymer electrolyte membrane of this example was prepared in the same manner as in example 1, except that SAS was used instead of AMPS.
Example 4
Adding 35g of AA monomer and 540g of deionized water into a glass reaction bottle provided with a stirring, heating and condensing device, adding 21g of LiOH to neutralize AA under stirring, introducing nitrogen to remove oxygen for 0.5 hour, heating to 60 ℃, adding 4g of 10% ammonium persulfate aqueous solution, simultaneously starting to dropwise add 65g of AN monomer, dropwise adding the monomer for about 3-5 hours, and then keeping the temperature for continuous reaction for 5 hours.
Adding 12g of AMPS, 25g of MA and 100g of dioxane solution with 60% of BCEAM concentration into the synthesized AA-AN copolymer aqueous solution, adding 10g of 10% ammonium persulfate aqueous solution and 150g of deionized water, and raising the temperature to 70-75 ℃ for reaction for 4-6 hours to obtain the polymer copolymerization emulsion with the solid content of about 20%.
10g of the copolymer emulsion was weighed and poured into a plastic vessel, the water was first dried in a blowing oven at 80 to 90℃and then transferred into a vacuum oven to be dried at 85 to 90℃for 24 hours, then a sample having a thickness of about 0.5mm was immersed into an electrolyte for a conventional lithium ion battery, and the liquid absorption and the electrical conductivity of the polymer electrolyte membrane were measured after immersing at 70℃for 24 hours by the electrolyte, as shown in Table 1.
Example 5
Adding 35g of AA monomer and 540g of deionized water into a glass reaction bottle provided with a stirring, heating and condensing device, adding 21g of LiOH to neutralize AA under stirring, introducing nitrogen to remove oxygen for 0.5 hour, heating to 60 ℃, adding 4g of 10% ammonium persulfate aqueous solution, simultaneously starting to dropwise add 65g of AN monomer, dropwise adding the monomer for about 3-5 hours, and then keeping the temperature for continuous reaction for 5 hours.
24g of AMPS, 50g of MA and 200g of dioxane solution with 60% of BCEAM concentration are added into the synthesized AA-AN copolymer aqueous solution, 20g of 10% ammonium persulfate aqueous solution and 200g of deionized water are added, and the temperature is raised to 70-75 ℃ for reaction for 4-6 hours, so that the polymer copolymerization emulsion with the solid content of about 25% is obtained.
10g of the copolymer emulsion was weighed and poured into a plastic vessel, the water was first dried in a blowing oven at 80 to 90℃and then transferred into a vacuum oven to be dried at 85 to 90℃for 24 hours, then a sample having a thickness of about 0.5mm was immersed into an electrolyte for a conventional lithium ion battery, and the liquid absorption and the electrical conductivity of the polymer electrolyte membrane were measured after immersing at 70℃for 24 hours by the electrolyte, as shown in Table 1.
Example 6
The polymer electrolyte membrane of this example was prepared in the same manner as in example 4, except that isooctyl acrylate was used instead of methyl acrylate.
Example 7
The polymer electrolyte membrane of this example was prepared in the same manner as in example 4, except that vinyl acetate was used instead of methyl acrylate.
Example 8
The polymer electrolyte membrane of this example was prepared in the same manner as in example 1 except that the amounts of the AA monomer and the AN monomer were 30g and 70g, respectively.
Example 9
The polymer electrolyte membrane of this example was prepared in the same manner as in example 1 except that the amounts of the AA monomer and the AN monomer were 40g and 60g, respectively.
TABLE 1 Polymer electrolyte Membrane electrolyte absorption Rate and conductivity
| Examples | Electrolyte absorptivity% | Conductivity Scm -1 |
| Example 1 | 131.2 | 1.9×10 -4 |
| Example 2 | 127.5 | 2.4×10 -4 |
| Example 3 | 143.4 | 2.2×10 -4 |
| Example 4 | 176.4 | 7.2×10 -4 |
| Example 5 | 210.6 | 9.8×10 -4 |
| Example 6 | 153.5 | 6.8×10 -4 |
| Example 7 | 166.3 | 4.8×10 -4 |
| Example 8 | 150.8 | 1.6×10 -4 |
| Example 9 | 121.7 | 1.1×10 -4 |
In conclusion, the electrolyte membrane is suitable for a dimethyl carbonate and diethyl carbonate electrolyte system, and has the liquid absorption rate of less than 250 percent and the ionic conductivity of 10 -4 ～10 -3 Scm -1 The polymer electrolyte membrane has good mechanical strength and elastic deformation due to low liquid absorption rate, and can be used as polymer electrolyte to replace liquid electrolyte so as to improve the safety performance of the lithium ion battery.
Claims (10)
1. A nitrile polymer electrolyte matrix material characterized in that: the catalyst is prepared by free radical polymerization of acrylonitrile-acrylic acid copolymer, sulfonate organic monomer with double bond and reaction monomer, wherein the reaction monomer comprises N, N-diethyl cyanoacrylamide;
the acrylonitrile-acrylic acid copolymer is polymerized by acrylonitrile monomers and acrylic acid monomers;
the sulfonate organic monomer with double bonds comprises at least one of sodium vinylsulfonate, sodium allylsulfonate, sodium methallylsulfonate, 2-acrylamide-2-methylpropanesulfonic acid and sodium p-styrenesulfonate;
the weight of the sulfonate organic monomer with double bonds is 5.0-20% of the weight of N, N-diethyl cyanoacrylamide; the weight of the reaction monomer is 50-300% of the weight of the acrylonitrile-acrylic acid copolymer.
2. The nitrile polymer electrolyte matrix material according to claim 1, characterized in that: the weight of the sulfonate organic monomer with double bonds is 14.0-20% of the weight of N, N-diethyl cyanoacrylamide; the weight of the reaction monomer is 80-170% of the weight of the acrylonitrile-acrylic acid copolymer.
3. The nitrile polymer electrolyte matrix material according to claim 1, characterized in that: the acrylonitrile monomer comprises at least one of acrylonitrile and methacrylonitrile, and the acrylic monomer comprises at least one of acrylic acid and methacrylic acid.
4. The nitrile polymer electrolyte matrix material according to claim 1, characterized in that: the weight ratio of the acrylic monomer to the acrylonitrile monomer is 25-40 percent and 60-75 percent.
5. The nitrile polymer electrolyte matrix material according to claim 4, wherein: the weight ratio of the acrylic monomer to the acrylonitrile monomer is 30-40 percent and 60-70 percent.
6. The nitrile polymer electrolyte matrix material according to claim 4, wherein: the acrylonitrile-acrylic acid copolymer is prepared by the following method: mixing water and acrylic monomers, regulating the pH to 7-9, heating to 50-70 ℃, adding an initiator, and beginning to dropwise add acrylonitrile monomers for polymerization reaction for 8-24 hr to obtain the acrylic polymer.
7. The nitrile polymer electrolyte matrix material according to claim 1, characterized in that: the reaction monomer also comprises acrylic ester monomer, and the weight ratio of N, N-diethyl cyanoacrylamide to acrylic ester monomer is 60-90 percent, 10-40 percent.
8. The nitrile polymer electrolyte matrix material according to claim 7, wherein: the chemical general formula of the acrylic ester monomer is CH 2 ＝CR 1 COOR 2 At least one of (1), wherein R 1 is-H or-CH 3 ，R 2 Is- (CH) 2 ) n CH 3 N is an integer of 0 to 12.
9. Nitrile polymer electrolyte comprising a polymer matrix and an electrolyte lithium salt, characterized in that: the polymer matrix is the nitrile polymer electrolyte matrix material according to any one of claims 1 to 8.
10. A gel polymer battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that: the electrolyte is the nitrile polymer electrolyte according to claim 9.
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| CN1784772A (en) * | 2003-05-08 | 2006-06-07 | 3M创新有限公司 | Organic polymers,laminates and capacitors |
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| CN106220779A (en) * | 2016-08-17 | 2016-12-14 | 四川茵地乐科技有限公司 | Acrylonitrile copolymer binder and the application in lithium ion battery thereof |
| CN106356527A (en) * | 2015-07-21 | 2017-01-25 | 成都茵地乐电源科技有限公司 | Polymer modified lithium cobalt oxide material for lithium ion battery, as well as preparation and application of polymer modified lithium cobalt oxide material |
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| US2798059A (en) * | 1956-03-21 | 1957-07-02 | American Cyanamid Co | Compositions comprising an acrylonitrile polymer and an nu-(2-cyanoethyl) acrylamide |
| CN1784772A (en) * | 2003-05-08 | 2006-06-07 | 3M创新有限公司 | Organic polymers,laminates and capacitors |
| CN102702657A (en) * | 2012-06-04 | 2012-10-03 | 常州中科来方能源发展有限公司 | Ionic polymer film material and preparation method thereof, and lithium secondary battery |
| CN102993891A (en) * | 2012-11-22 | 2013-03-27 | 中航锂电（洛阳）有限公司 | Paint for lithium ion battery composite membrane and composite membrane using coating |
| CN106356527A (en) * | 2015-07-21 | 2017-01-25 | 成都茵地乐电源科技有限公司 | Polymer modified lithium cobalt oxide material for lithium ion battery, as well as preparation and application of polymer modified lithium cobalt oxide material |
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