CN114551996B - Cyclophosphazene modified flame-retardant polymer electrolyte and preparation method thereof - Google Patents
Cyclophosphazene modified flame-retardant polymer electrolyte and preparation method thereof Download PDFInfo
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- CN114551996B CN114551996B CN202210044266.0A CN202210044266A CN114551996B CN 114551996 B CN114551996 B CN 114551996B CN 202210044266 A CN202210044266 A CN 202210044266A CN 114551996 B CN114551996 B CN 114551996B
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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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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a cyclophosphazene modified flame-retardant polymer electrolyte and a preparation method thereof, wherein the flame-retardant polymer electrolyte comprises the following components: the flame retardant comprises a cyclophosphazene, a plasticizer, a polymer substrate, a glass fiber membrane framework and lithium salt, wherein the flame retardant and the polymer substrate are polymerized under illumination through a photoinitiator to form a crosslinked network structure. The beneficial effects of the invention are as follows: by utilizing ultraviolet polymerization and using cyclophosphazene modified solid polymer electrolyte, the electrochemical performance is ensured and the flame-retardant effect is increased under the condition of hardly influencing the ion transmission performance, so that the guarantee is provided for preparing the high-safety lithium ion battery.
Description
Technical Field
The invention relates to the field of polymer electrolytes, in particular to a flame-retardant polymer electrolyte modified by cyclophosphazene and a preparation method thereof.
Background
With the increasing emphasis on renewable energy sources, lithium ion batteries have attracted attention as efficient energy storage devices with potential for development in the marketplace. High-safety lithium ion batteries realizing high energy density and quick charge are necessarily developed in the future. Among them, solid-state lithium ion batteries are considered as one of the most promising developments, and solid-state electrolytes have been widely studied and paid attention as core members of solid-state batteries. Solid electrolyte batteries are classified into inorganic solid electrolytes, organic polymer solid electrolytes and composite solid electrolytes. Among them, the organic polymer solid electrolyte has the advantages of high ionic conductivity, simple preparation process and good flexibility, so that the organic polymer solid electrolyte is used as one of the break-through openings for research. However, the polymer has the risk of being flammable, and is particularly applied to the field of batteries, and safety accidents can be caused when thermal runaway exists.
Accordingly, it is necessary to provide a polymer electrolyte having an excellent flame retardant effect to overcome the above problems.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides a cyclophosphazene modified flame-retardant polymer electrolyte and a preparation method thereof. According to the scheme, under the condition that the ion transmission performance is not affected, the electrochemical performance is ensured, and meanwhile, the flame-retardant effect is improved.
To achieve the above object, a first aspect of the present invention is to provide a flame retardant polymer electrolyte modified with cyclophosphazene. The composition comprises the following components: the flame retardant comprises a cyclophosphazene, a plasticizer, a polymer substrate, a glass fiber membrane framework and lithium salt, wherein the flame retardant and the polymer substrate are polymerized under illumination through a photoinitiator to form a crosslinked network structure.
The polymer substrate is one or more of polymethyl acrylate, polypropylene carbonate, polypropylene oxide, polymethacrylate and polycarbonate.
Further provided that the lithium salt is LiPF 6 、LiF 4 、LiCLO 4 One or more of LiTf, liFSI, liTFSI, liBOB, liODFB.
The mass ratio of the total amount of the plasticizer and the lithium salt to the polymer substrate is 20:1-1:1.
The photoinitiator is further arranged to account for 0.1-10% of the mass ratio of the polymer monomers.
Further, the thickness of the glass fiber film is 10 to 1000 μm.
The further arrangement is that: the plasticizer is succinonitrile.
The second aspect of the invention provides a preparation method of the flame-retardant polymer electrolyte, which comprises the following steps:
(1) Dissolving a plasticizer and lithium salt, adding a polymer substrate, a flame retardant and a photoinitiator, and uniformly stirring to obtain a mixed solution;
(2) And (3) coating the mixed solution obtained in the step (1) in a glass fiber membrane, and irradiating with ultraviolet light to polymerize the polymer substrate and the flame retardant, so as to finally obtain the cyclophosphazene modified flame retardant polymer electrolyte.
The stirring speed of the step (1) is 100-1000 rpm, the dissolution temperature of the plasticizer and the lithium salt is 30-100 ℃, and the irradiation time of ultraviolet light is 30 s-1 h.
In addition, the invention also provides an application of the pentachloroxycyclotriphosphazene modified flame retardant polymer electrolyte in lithium ion batteries as an electrolyte.
The beneficial effects of the invention are as follows:
by utilizing ultraviolet polymerization and using cyclophosphazene modified solid polymer electrolyte, the electrochemical performance is ensured and the flame-retardant effect is increased under the condition of hardly influencing the ion transmission performance, so that the guarantee is provided for preparing the high-safety lithium ion battery. The added cyclophosphazene has good heat stability and flame retardance. When heated, the flame retardant material releases free radicals with flame retardant property, and prevents continuous reaction of hydroxyl free radicals, thereby achieving the flame retardant effect. The lithium ion battery can be used in a lithium ion battery, so that the safety performance of the battery can be effectively improved.
See the figure for specific experimental data.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a plan and cross-sectional Scanning Electron Microscope (SEM) view of a solid polymer electrolyte prepared using the present invention;
FIG. 2 is a Cyclic Voltammogram (CV) of a solid polymer electrolyte prepared using example 1 of the present invention;
FIG. 3 is a charge-discharge curve of a voltage range of 2.5V to 4.0V in a lithium iron phosphate half cell using the solid polymer electrolyte prepared in example 2 of the present invention;
FIG. 4 is a graph showing the magnification of the solid polymer electrolyte prepared in example 2 according to the present invention in the range of 0.1C to 2C at a voltage of 2.5V to 4.0V in a lithium iron phosphate half cell;
FIG. 5 is a graph showing the results of a combustion test of the solid polymer electrolyte prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Examples1
(a1) 8.5g of hexachlorocyclotriphosphazene and 40.0g of anhydrous K 2 CO 3 Adding into proper amount of acetone for dissolution. 3.5g of a 2-allylphenol solution was added dropwise thereto, and the reaction was carried out at reflux under elevated temperature for 2.5 hours. After cooling, 12.0g of phenol dissolved in acetone was added thereto, and the mixture was refluxed for 7 hours at a temperature. Cooling, filtering, distilling the filtrate to recover solvent, dissolving with proper amount of toluene, sequentially washing with low-concentration NaOH, HCL and distilled water to neutrality, drying, filtering, and removing solvent to obtain the pentaphenoxy cyclotriphosphazene APPCP.
(a2) 1M lithium bis (trifluoromethanesulfonyl) sulfide LiTFSI is added to succinonitrile SN to dissolve at 70 ℃, and ethoxylated trimethylolpropane triacrylate ETPTA, pentaphenoxy cyclotriphosphazene APPCP and 2-hydroxy-2-methylpropionacetone HMPP are added to stir for 20min. Wherein the mass ratio of the total mass of LiTFSI and SN to ETPTA is 8:1, and the mass ratio is APPCP: etpta=1:20, hmpp accounts for 0.2% of the mass of ETPTA.
(a3) And coating the obtained mixed solution in a glass fiber film, and irradiating with ultraviolet light for 5min to obtain the pentachloroxycyclotriphosphazene modified flame retardant polymer electrolyte.
Examples2
(a1) 8.5g of hexachlorocyclotriphosphazene and 40.0g of anhydrous K 2 CO 3 Adding into proper amount of acetone for dissolution. 3.5g of a 2-allylphenol solution was added dropwise thereto, and the reaction was carried out at reflux under elevated temperature for 2.5 hours. After cooling, 12.0g of benzene dissolved in acetone was addedPhenol, temperature rise and reflux for 7h. Cooling, filtering, distilling the filtrate to recover solvent, dissolving with proper amount of toluene, sequentially washing with low-concentration NaOH, HCL and distilled water to neutrality, drying, filtering, and removing solvent to obtain the pentaphenoxy cyclotriphosphazene APPCP.
(a2) 1M lithium bis (trifluoromethanesulfonyl) sulfide LiTFSI is added to succinonitrile SN to dissolve at 70 ℃, and ethoxylated trimethylolpropane triacrylate ETPTA, pentaphenoxy cyclotriphosphazene APPCP and 2-hydroxy-2-methylpropionacetone HMPP are added to stir for 20min. Wherein the mass ratio of the total mass of LiTFSI and SN to ETPTA is 8:1, and the mass ratio is APPCP: etpta=1:15, hmpp accounting for 0.2% of ETPTA mass
(a3) And coating the obtained mixed solution in a glass fiber film, and irradiating with ultraviolet light for 5min to obtain the pentachloroxycyclotriphosphazene modified flame retardant polymer electrolyte.
Examples3
(a1) 8.5g of hexachlorocyclotriphosphazene and 40.0g of anhydrous K 2 CO 3 Adding into proper amount of acetone for dissolution. 3.5g of a 2-allylphenol solution was added dropwise thereto, and the reaction was carried out at reflux under elevated temperature for 2.5 hours. After cooling, 12.0g of phenol dissolved in acetone was added thereto, and the mixture was refluxed for 7 hours at a temperature. Cooling, filtering, distilling the filtrate to recover solvent, dissolving with proper amount of toluene, sequentially washing with low-concentration NaOH, HCL and distilled water to neutrality, drying, filtering, and removing solvent to obtain the pentaphenoxy cyclotriphosphazene APPCP.
(a2) 1M lithium bis (trifluoromethanesulfonyl) sulfide LiTFSI is added to succinonitrile SN to dissolve at 70 ℃, and ethoxylated trimethylolpropane triacrylate ETPTA, pentaphenoxy cyclotriphosphazene APPCP and 2-hydroxy-2-methylpropionacetone HMPP are added to stir for 20min. Wherein the mass ratio of the total mass of LiTFSI and SN to ETPTA is 8:1, and the mass ratio is APPCP: etpta=1:10, hmpp accounts for 0.2% of the mass of ETPTA.
(a3) And coating the obtained mixed solution in a glass fiber film, and irradiating with ultraviolet light for 5min to obtain the pentachloroxycyclotriphosphazene modified flame retardant polymer electrolyte.
Examples4
(a1) 8.5g of hexachlorocyclotriphosphazene and 40.0g of aganude are reactedWater K 2 CO 3 Adding into proper amount of acetone for dissolution. 3.5g of a 2-allylphenol solution was added dropwise thereto, and the reaction was carried out at reflux under elevated temperature for 2.5 hours. After cooling, 12.0g of phenol dissolved in acetone was added thereto, and the mixture was refluxed for 7 hours at a temperature. Cooling, filtering, distilling the filtrate to recover solvent, dissolving with appropriate amount of toluene, sequentially washing with low concentration NaOH and HCL and distilled water to neutrality, drying, filtering, and removing solvent to obtain pentaphenoxy cyclotriphosphazene APPCP
(a2) 1M lithium bis (trifluoromethanesulfonyl) sulfide LiTFSI is added to succinonitrile SN to dissolve at 70 ℃, and ethoxylated trimethylolpropane triacrylate ETPTA, pentaphenoxy cyclotriphosphazene APPCP and 2-hydroxy-2-methylpropionacetone HMPP are added to stir for 20min. Wherein the mass ratio of the total mass of LiTFSI and SN to ETPTA is 8:1, and the mass ratio is APPCP: etpta=1:5, hmpp accounts for 0.2% of the mass of ETPTA.
(a3) And coating the obtained mixed solution in a glass fiber film, and irradiating with ultraviolet light for 5min to obtain the pentachloroxycyclotriphosphazene modified flame retardant polymer electrolyte.
Examples5
This example 5 differs from example 1 in that the lithium bistrifluoromethylsulfonimide LiTFSI is replaced with: liPF (LiPF) 6 、LiF 4 、LiCLO 4 Either of LiTf, liFSI, liBOB, liODFB, the other preparation conditions were the same.
Examples6
This example 6 differs from example 1 in that the ethoxylated trimethylolpropane triacrylate ETPTA is replaced with one of polymethyl acrylate, polypropylene carbonate, polypropylene oxide, polymethacrylate, and polycarbonate, with the other preparation conditions being the same.
Examples7
This example 7 differs from example 1 in that the pentachloroxycyclotriphosphazene APPCP is replaced with any one of other cyclic phosphazenes such as ethoxypentafluoroetriphosphazene, phenoxypentafluoroetriphosphazene, hexaallylaminotriphosphazene, and the like, and other preparation conditions are the same.
Application example
The flame retardant polymer electrolyte prepared in the above example of the present invention was used as an electrolyte of a lithium battery.
The experimental effect shows that:
the cyclophosphazene modified flame-retardant polymer electrolyte has excellent flame-retardant performance, can still be maintained for a period of time without burning under the condition of encountering open fire, and improves the safety of the electrolyte (figure 5). The electrolyte showed a fast lithium ion transport by its CV curve at 0.2mV/s sweep rate, and the kinetic properties were not affected by the addition of flame retardant (FIG. 2). Meanwhile, the electrolyte shows a wide electrochemical window and voltage range when being matched with a lithium iron phosphate anode. And can be kept stable in charge-discharge cycle within the voltage range of 2.5V-4.0V, has smaller polarization and high specific capacity, and can still keep 140mAh/g for multiple cycles, thus indicating that the electrolyte is favorable for lithium ion transmission (figure 3). Meanwhile, the lithium ion battery can be stably charged and discharged under high multiplying power, the specific charge of the lithium ion battery can reach 140mAh/g under 2C multiplying power, the ion transmission is rapid, the side reaction is less, and the lithium ion battery can be quickly charged in the future (figure 4).
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (8)
1. A cyclophosphazene modified flame retardant polymer electrolyte characterized by comprising the following components: the flame retardant comprises a flame retardant, a plasticizer, a polymer substrate, a glass fiber membrane framework and lithium salt, wherein the flame retardant is cyclophosphazene, and the flame retardant and the polymer substrate are polymerized under the irradiation of light through a photoinitiator to form a crosslinked network structure;
the mass ratio of the total amount of the plasticizer and the lithium salt to the polymer substrate is 20:1-1:1, and the photoinitiator accounts for 0.1-10% of the mass ratio of the polymer monomer;
the thickness of the glass fiber film is 10-1000 mu m.
2. The cyclophosphazene modified flame retardant polymer electrolyte of claim 1, characterized in that: the polymer substrate is one or a mixture of more of polymethyl acrylate, polypropylene carbonate, polypropylene oxide, polymethacrylate, polyacrylate and ethoxylated trimethylolpropane triacrylate.
3. The cyclophosphazene modified flame retardant polymer electrolyte of claim 1, characterized in that: the lithium salt is LiPF 6 、LiF 4 、LiCLO 4 One or more of LiTf, liFSI, liTFSI, liBOB, liODFB.
4. The cyclophosphazene modified flame retardant polymer electrolyte of claim 1, characterized in that: the plasticizer is succinonitrile.
5. The cyclophosphazene modified flame retardant polymer electrolyte of claim 1, characterized in that: the cyclophosphazene is pentachenoxy cyclophosphazene, ethoxy pentafluoroethylene cyclophosphazene, phenoxy pentafluoroethylene cyclophosphazene or hexaallylamine cyclophosphazene.
6. The method for producing a flame retardant polymer electrolyte according to any one of claims 1 to 5, characterized by comprising the steps of:
dissolving a plasticizer and lithium salt, adding a polymer substrate, a flame retardant and a photoinitiator, and uniformly stirring to obtain a mixed solution;
(2) And (3) coating the mixed solution obtained in the step (1) in a glass fiber membrane, and irradiating with ultraviolet light to polymerize the polymer substrate and the flame retardant, so as to finally obtain the cyclophosphazene modified flame retardant polymer electrolyte.
7. The method of manufacturing according to claim 6, wherein: the stirring speed of the step (1) is 100-1000 rpm, the dissolution temperature of the plasticizer and the lithium salt is 30-100 ℃, and the ultraviolet irradiation time is 30 s-1 h.
8. Use of the cyclophosphazene modified flame retardant polymer electrolyte of claim 1 as an electrolyte in a lithium ion battery.
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