CN111900465A - POSS-based polyion liquid solid electrolyte membrane and preparation method of material thereof - Google Patents
POSS-based polyion liquid solid electrolyte membrane and preparation method of material thereof Download PDFInfo
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 97
- 239000007788 liquid Substances 0.000 title claims abstract description 85
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims description 61
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 40
- 239000005518 polymer electrolyte Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 27
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- -1 methacryloyl Chemical group 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 239000011344 liquid material Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000002883 imidazolyl group Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001347 alkyl bromides Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- WTVNABTWDZCYCN-UHFFFAOYSA-N hexane;hydrobromide Chemical compound Br.CCCCCC WTVNABTWDZCYCN-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- KXGYGLSAOVEXPN-UHFFFAOYSA-N pentane;hydrobromide Chemical compound Br.CCCCC KXGYGLSAOVEXPN-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000348 solid-phase epitaxy Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Images
Classifications
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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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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 discloses a POSS-based polyion liquid solid electrolyte membrane and a preparation method thereof. And mixing the POSS-based polyionic liquid, PVDF-HFP, lithium salt and the ionic liquid, pouring the mixture into a mold after uniformly stirring, and drying to obtain the solid electrolyte membrane. The electrolyte has the advantages of high thermal stability, good film forming property, no flammability and no liquid leakage, can greatly improve the safety performance of the lithium ion battery, has high ionic conductivity, wide electrochemical window, good compatibility with electrode materials and excellent cyclicity and multiplying power performance, and can be applied to the field of the lithium ion battery.
Description
Technical Field
The invention relates to preparation of a solid polymer electrolyte, in particular to a POSS-based polyion liquid solid polymer electrolyte membrane and a preparation method thereof.
Background
Solid polymer electrolytes have many advantages as ideal substitutes for liquid electrolytes, such as non-volatility, no leakage, high energy density, safety, and the like. However, the solid polymer electrolyte has low room-temperature ionic conductivity and mechanical strength, which limits the popularization and application. The ionic liquid has the advantages of higher conductivity, lower vapor pressure, wider electrochemical window, liquid stability range and the like, and is often widely applied to solid electrolyte as a plasticizer to improve the conductivity of the solid electrolyte. However, the ionic liquid or the electrolyte prepared by simply and physically mixing the ionic liquid with the polymer after the ionic liquid is polymerized has the problems of poor compatibility and film forming property. The polyion liquid obtained by grafting the ionic liquid or polymerizing the ionic liquid and a polymer monomer has the characteristics of the ionic liquid and the stability of a polymer, and has good application prospect in the aspect of preparing solid polymer electrolytes.
Silsesquioxane (POSS) as an organic-inorganic nano hybrid material has unique advantages in improving the thermal stability, ionic conductivity and ion migration number of solid polymer electrolyte due to the unique silicon core cage structure, and the organic part can also improve the compatibility with polymers. Currently POSS is mainly doped physicallyOr copolymerize with polymer monomers to prepare polymer electrolytes, still suffer from low room temperature ionic conductivity. For example, a dendritic copolymer BCP is prepared by taking polyethylene glycol dimaleate monoester (PEGMA) and heptaisobutyl methacryloyl POSS (MAPOSS) as monomers and Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent, SPEs is prepared by taking a matrix of the BCP and LiTFSI as a lithium salt by a pouring method, the SPEs has better dimensional stability, an electrolyte system has good electrochemical stability, and the ionic conductivity at 30 ℃ reaches 10- 5Scm-1(Polymer Chemistry,2014,5(10): 3432-. Therefore, the POSS-containing polyionic liquid designed and synthesized by combining the advantages of the polyionic liquid and the POSS can be used for preparing novel solid electrolytes. In the current research, most of POSS combined with ionic liquid is octafunctional group POSS with higher activity, and a monofunctional group is difficult to polymerize with ionic liquid monomers due to lower activity and larger resistance, for example, the monofunctional group POSS is difficult to polymerize with N-vinyl imidazole ionic liquid monomers, and the ionic conductivity is not ideal.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a POSS-based polyion liquid solid electrolyte membrane and a preparation method of the material thereof, so that the POSS-based polyion liquid solid electrolyte membrane capable of improving ionic conductivity and lithium ion transference number and improving battery cycle rate performance can be provided, and the problems of poor compatibility and film forming property of ionic liquid and polymer and easy overflow of ionic liquid in the existing physical mixing method can be better solved. The electrolyte material has the advantages of high thermal stability, good film forming property, no flammability and no leakage, and can greatly improve the safety performance of the lithium ion battery. Has high ionic conductivity, wide electrochemical window, good compatibility with electrode materials, excellent cyclicity and rate capability, and can be applied to the field of lithium ion batteries.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a POSS-based polyion liquid solid electrolyte material comprises the following steps:
(1) synthesis of POSS-based polyion liquid material:
a. adding an initiator into a toluene or isopropanol solution of an N-vinyl imidazole monomer (VIm), stirring under the protection of nitrogen, carrying out reflux reaction at 60-80 ℃, immediately adding a toluene or isopropanol solution of a heptaisobutyl methacryloyl POSS Monomer (MAPOSS) when a white precipitate is generated, continuously reacting for at least 12h, carrying out suction filtration on the product solution, washing for at least 2 times by using toluene or isopropanol, and drying to obtain a polymer P [ MAPOSS-VIm ] white solid; the yield is 91-97%;
the mass ratio of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) to the N-vinylimidazole monomer (VIm) is 1:3-1: 10;
the concentration of the toluene or isopropanol solution of the N-vinyl imidazole monomer (VIm) is 2-3 mol/L;
the concentration of the toluene or isopropanol solution of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) is 0.1-0.2 mol/L;
b. dissolving the polymer P [ MAPOSS-VIm ] obtained in the step a in an ethanol solvent to obtain an ethanol solution of the polymer P; calculating the theoretical substance amount of imidazole ring according to the charge ratio of N-vinyl imidazole monomer (VIm) and heptaisobutyl methacryloyl POSS Monomer (MAPOSS), weighing bromoalkane with the amount of 1-2 times of the imidazole ring substance, dripping into the ethanol solution of the polymer P at a speed of not more than 2 drops per second under the conditions of ice water bath and nitrogen protection, after the dropwise addition, the mixed solution is continuously stirred for 4-7 days at room temperature for reaction, when the reaction is finished, partial ethanol solvent is removed by rotary evaporation, ethyl acetate is continuously dropwise added into the obtained product solution until no solid is precipitated, then carrying out suction filtration on the product solution, washing the product solution for at least 2 times by using ethyl acetate, then carrying out vacuum drying on the collected product for at least 24h at the temperature of 60-70 ℃, thus obtaining a light yellow powder solid product P [ MAPOSS-VIm ] [ Br ]; the yield is 70-75%;
c. dissolving the P [ MAPOSS-VIm ] [ Br ] obtained in the step b in N, N-Dimethylformamide (DMF), weighing lithium bistrifluoromethanesulfonylimide (LiTFSI) with the molar ratio equal to the bromide ion of the P [ MAPOSS-VIm ] [ Br ] and dissolving the lithium bistrifluoromethanesulfonylimide (LiTFSI) in water, dropping the aqueous solution of lithium salt into the DMF solution of the P [ MAPOSS-VIm ] [ Br ] at the speed of no less than two drops per second, and continuously and violently stirring the mixed solution at room temperature for no more than 24 hours to react after the dropping is finished; along with the reaction, a large amount of solid is continuously separated out; after the reaction is finished, carrying out suction filtration on the product solution, washing for at least 2 times by using deionized water, and carrying out vacuum drying for at least 24h at 60-80 ℃ to obtain a faint yellow powdery solid P [ MAPOSS-VIm ] [ TFSI ], so as to obtain a POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ]; the yield is 91-96%;
(2) preparation of solid polymer electrolyte material:
2-4.5g of POSS-based polyionic liquid material P [ MAPOSS-VIm ] [ TFSI ] and 1.5-2.0g of poly (vinylidene fluoride-hexafluoropropylene) (P (VDF-HFP)), 0-3g of room temperature ionic liquid and 0.5-2.0g of lithium bistrifluoromethanesulfonylimide (LiTFSI) are dissolved in 5-12ml of DMF or DMSO solvent, stirred at 70-90 ℃, and uniformly mixed to obtain solid polymer electrolyte slurry, the solid polymer electrolyte slurry is poured into a polytetrafluoroethylene mold, defoamed in a vacuum oven at 60-90 ℃, dried for 10-30h, and then the solvent is removed to obtain the solid polymer electrolyte material.
In the step (1), the initiator is at least one of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile, azobiscyclohexylnitrile, benzoyl peroxide, lauroyl peroxide and potassium persulfate.
As a preferable technical scheme of the invention, in the step (1), the amount of the initiator is 0.1-1.2% of the total mass of the N-vinylimidazole monomer (VIm) and the heptaisobutylmethacryloyl POSS Monomer (MAPOSS).
As a preferable technical solution of the present invention, in the step (1), the alkyl bromide is at least one of ethyl bromide, n-propyl bromide, n-butyl bromide, pentane bromide and n-hexane bromide.
As a preferable technical scheme of the invention, in the step (1), reflux reaction is carried out at 65-80 ℃; the mass ratio of the heptaisobutylmethacryloyl POSS Monomer (MAPOSS) to the N-vinylimidazole monomer (VIm) is 1:5-1: 10; the concentration of the toluene or isopropanol solution of the N-vinyl imidazole monomer (VIm) is 2.656-3 mol/L; the concentration of the toluene or isopropanol solution of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) is 0.14-0.20 mol/L; weighing bromoalkane which is 1.2 to 1.8 times of the amount of imidazole ring substances in the heptaisobutylmethacryloyl POSS Monomer (MAPOSS) and the N-vinyl imidazole monomer (VIm); adding lithium bistrifluoromethanesulfonimide (LiTFSI) and stirring the mixed solution at room temperature for 2-24 h.
In the step (2), 1-methyl-3-propyl imidazole bis (trifluoromethyl) sulfonyl imide salt or 1-butyl-3-methyl imidazole bis (trifluoromethyl) sulfonyl imide salt is used as the room-temperature ionic liquid.
In the step (2), 2-4g of POSS-based polyionic liquid material P [ MAPOSS-VIm ] [ TFSI ] and 1.5-2.0g of poly (vinylidene fluoride-hexafluoropropylene) (P (VDF-HFP)), 2-3g of room temperature ionic liquid and 1.2-1.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) are dissolved in 10-12ml of DMF or DMSO solvent, and are uniformly stirred at 80-90 ℃ to obtain solid polymer electrolyte slurry.
The invention discloses a POSS-based polyion liquid solid electrolyte membrane, which is prepared by adopting the preparation method of the POSS-based polyion liquid solid electrolyte membrane.
As a preferable technical scheme, the preparation method of the POSS-based polyion liquid solid electrolyte material is adopted to prepare the solid polymer electrolyte material, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicing machine.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention overcomes the problem that the monomer of the POSS and the N-vinyl imidazole ionic liquid with single functional group is difficult to polymerize, and the POSS and the N-vinyl imidazole are polymerized and then further prepared into the POSS-based ionic liquid, so that the reaction is easy to carry out, the method is simple, and the POSS-based polyionic liquid with high purity and high yield can be obtained;
2. the invention selects POSS-based polyion liquid and P(VDF-HFP) is taken as a matrix, an interpenetrating network structure can be formed during film forming, the prepared POSS-based polyion liquid solid electrolyte membrane has good mechanical strength and flexibility, and the electrochemical stability window can reach more than 4.7V; the ion conductivity measured at room temperature can reach 10-4S/cm; the transference number of lithium ions is 0.3; assembled Li/POSS-PIL-SPE/LiFePO4The formed half cell has stable cycling rate performance, and the charge-discharge capacity can reach 153mAh/g at 0.1 ℃;
3. in the preparation process of the ionic liquid-carbon material/polyurethane film, all reagents are commercial products and do not need further treatment; the method is simple and easy to implement, mild in condition, low in cost and suitable for popularization and use.
Drawings
FIG. 1 is a diagram of a POSS-based polyionic liquid solid electrolyte membrane according to the present invention.
Figure 2 is a graph of the cycling performance of a cell assembled using the POSS-based polyionic liquid solid electrolyte membrane of example 3.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) synthesis of POSS-based polyion liquid material:
a. weighing 10g (106.2mmol) of 1-vinylimidazole, adding the 1-vinylimidazole into a 250mL single-neck round-bottom flask containing 40mL of isopropanol, adding 0.12g of 2, 2-azobisisobutyronitrile after complete dissolution, magnetically stirring at 65 ℃, and carrying out reflux reaction under the protection of nitrogen; as the reaction proceeded, when a white substance was generated, a 15mL isopropanol solution in which 2g (2.12mmol) of heptaisobutylmethacryloyl POSS was dissolved was immediately added, and the whole reaction was carried out under nitrogen protection; after 12h, stopping heating and stirring, carrying out suction filtration on the product solution to obtain a white powdery solid, washing the white powdery solid for at least 2 times by using isopropanol, removing unreacted heptaisobutyl methacryloyl POSS and 1-vinyl imidazole, and carrying out vacuum drying on the product at the temperature of 60 ℃ for 24 h; polymer P [ MAPOSS-VIm ] was obtained as a white solid; the yield was 92%;
b. weighing 10g of the polymer P [ MAPOSS-VIm ] obtained in step a to obtain an ethanol solution of the polymer P; wherein the theoretical substance of imidazole ring is 88.5mmol, adding into 500mL single-neck round-bottom flask containing 100mL ethanol, and performing ultrasonic treatment until completely dissolving; weighing 21.83(159.3mmol) n-butyl bromide in a constant pressure dropping funnel, dropping the n-butyl bromide into the ethanol solution at a speed of 2 drops per second under the conditions of ice water bath and nitrogen protection, after 30-40 minutes, finishing the dropping, and continuing stirring at room temperature for 1 week; after the reaction is finished, removing part of ethanol solvent by rotary evaporation, continuously dropwise adding ethyl acetate until no solid is separated out, then carrying out suction filtration on the product solution to obtain a light yellow powdery solid, and washing for at least 2 times by using ethyl acetate; then, the product is dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain faint yellow powder solid P [ MAPOSS-VIm ] [ TFSI ], thereby obtaining POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ]; the yield is 71%;
c. weighing 11.55g of P [ MAPOSS-VIm ] [ Br ] obtained in step b, wherein the amount of the substance of bromide ion is 46.2mmol, adding into a 500mL single-neck round-bottom flask containing 100mL of DMF, and performing ultrasonic treatment to completely dissolve; weighing 13.26g (46.2mmol) of lithium bistrifluoromethanesulfonylimide, adding the lithium bistrifluoromethanesulfonylimide into a 50mL single-neck round-bottom flask containing 20mL of deionized water, and performing ultrasonic treatment to completely dissolve the lithium bistrifluoromethanesulfonylimide to obtain an aqueous solution of lithium salt; and transferring the aqueous solution of lithium salt to a constant pressure dropping funnel; dropping the aqueous solution of lithium salt into DMF solution of P [ MAPOSS-VIm ] [ Br ] at a speed of two drops per second, and stirring for 2h at room temperature for reaction; along with the reaction, a large amount of solid is continuously separated out; after the reaction is finished, carrying out suction filtration on the product solution to obtain a light yellow powdery solid, and washing the light yellow powdery solid for at least 2 times by using deionized water to obtain a product; vacuum drying the product at 60 ℃ for 24h to obtain a faint yellow powdery solid P [ MAPOSS-VIm ] [ TFSI ], thereby obtaining a POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ]; the yield was 91.30%;
(2) preparation of solid polymer electrolyte material:
weighing 4.0g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 2.0g of P (VDF-HFP), 2.0g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.2g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the mixture in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the mixture in the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) the procedure was the same as in example 1;
(2) preparation of solid polymer electrolyte material:
weighing 4.0g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 2.0g of P (VDF-HFP), 2.5g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.2g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the mixture in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the mixture in the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3.
Example 3:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) the procedure was the same as in example 1;
(2) preparation of solid polymer electrolyte material:
weighing 4.0g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 2.0g of P (VDF-HFP), 3.0g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.2g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the mixture in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the mixture in the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3. Cycling performance fig. 2 is a graph of cycling performance of a cell assembled using the POSS-based polyionic liquid solid electrolyte membrane of this example, fig. 2 is a graph.
Example 4:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) synthesis of POSS-based polyion liquid material:
a. weighing 20g (212.5mmol) of 1-vinylimidazole, adding the 1-vinylimidazole into a 250mL single-neck round-bottom flask containing 80mL of toluene, adding 0.24g of 2, 2-azobisisobutyronitrile after complete dissolution, magnetically stirring at 65 ℃, and carrying out reflux reaction under the protection of nitrogen; as the reaction proceeded, when a white substance was generated, 15mL of a toluene solution in which 2g (2.12mmol) of heptaisobutylmethacryloyl POSS was dissolved was immediately added, and the whole reaction was carried out under nitrogen protection; after 12h, stopping heating and stirring, carrying out suction filtration on the product solution to obtain a white powdery solid, washing the white powdery solid for at least 2 times by using toluene, removing unreacted heptaisobutyl methacryloyl POSS and 1-vinyl imidazole, and carrying out vacuum drying on the product at the temperature of 60 ℃ for 24 h; polymer P [ MAPOSS-VIm ] was obtained as a white solid; the yield is 95%;
b. weighing 10g of the polymer P [ MAPOSS-VIm ] obtained in step a to obtain an ethanol solution of the polymer P; adding 177mmol of theoretical substances of imidazole ring into a 250mL single-neck round-bottom flask containing 60mL of ethanol, and performing ultrasonic treatment until the theoretical substances are completely dissolved; weighing 29.11g (212.4mmol) of n-butyl bromide in a constant pressure dropping funnel, dropping the n-butyl bromide into the ethanol solution at the speed of 2 drops per second under the conditions of ice water bath and nitrogen protection, after 30-40 minutes, finishing the titration, and continuing stirring at room temperature for 1 week; after the reaction is finished, removing part of ethanol solvent by rotary evaporation, continuously dropwise adding ethyl acetate until no solid is separated out, then carrying out suction filtration on the product solution to obtain a light yellow powdery solid, and washing for at least 2 times by using ethyl acetate; then, the product is dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain faint yellow powder solid P [ MAPOSS-VIm ] [ TFSI ], thereby obtaining POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ]; the yield was 73%;
c. weighing 12g of P [ MAPOSS-VIm ] [ Br ] obtained in step b, wherein the amount of the substance of bromide ion is 49.9mmol, adding the weighed substance into a 250mL single-neck round-bottom flask containing 55mL of DMF, and carrying out ultrasonic treatment to completely dissolve the substance; weighing 14.32g (49.9mmol) of lithium bistrifluoromethanesulfonylimide, adding the lithium bistrifluoromethanesulfonylimide into a 50mL single-neck round-bottom flask containing 20mL of deionized water, and performing ultrasonic treatment to completely dissolve the lithium bistrifluoromethanesulfonylimide to obtain an aqueous solution of lithium salt; and transferring the aqueous solution of lithium salt to a constant pressure dropping funnel; dropping the aqueous solution of lithium salt into DMF solution of P [ MAPOSS-VIm ] [ Br ] at a speed of two drops per second, and stirring for 2h at room temperature for reaction; along with the reaction, a large amount of solid is continuously separated out; after the reaction is finished, carrying out suction filtration on the product solution to obtain a light yellow powdery solid, and washing the light yellow powdery solid for at least 2 times by using deionized water to obtain a product; vacuum drying the product at 60 ℃ for 24h to obtain a faint yellow powdery solid P [ MAPOSS-VIm ] [ TFSI ], thereby obtaining a POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ]; the yield is 95%;
(2) preparation of solid polymer electrolyte material:
weighing 3.0g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 1.5g of P (VDF-HFP), 3.0g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the mixture in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the mixture in the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3.
Example 5:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) the procedure was the same as in example 4;
(2) preparation of solid polymer electrolyte material:
weighing 2.5g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 1.5g of P (VDF-HFP), 3.0g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the weighed materials in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3.
Example 6:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a POSS-based polyion liquid solid electrolyte material includes the following steps:
(1) the procedure was the same as in example 4;
(2) preparation of solid polymer electrolyte material:
weighing 2.0g of POSS-based polyionic liquid P [ MAPOSS-VIM ] [ TFSI ], 1.5g of P (VDF-HFP), 3.0g of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIM ] TFSI) and 1.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) prepared in the step (1), placing the weighed materials in a round-bottomed flask, adding 10mL of DMF, and stirring at 80 ℃ for 24h to completely dissolve the DMF; and pouring the uniformly stirred DMF solution into a clean polytetrafluoroethylene mold, and drying in a vacuum oven at 80 ℃ for 18 hours to remove the DMF solvent to obtain the solid polymer electrolyte material.
In this example, a POSS-based polyion liquid solid electrolyte membrane is prepared by the method of preparing the POSS-based polyion liquid solid electrolyte material according to this example, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicer. See fig. 1.
Experimental test analysis:
the solid polymer electrolyte material prepared in this example was subjected to experimental test analysis, see table 1. The POSS-based polyionic liquid solid electrolyte membrane prepared in this example was placed in a glove box for cell assembly and cell performance tests were performed see tables 2 and 3. Combining the test results of the above experiments of examples 1-6, see tables 1-3 below:
TABLE 1 Experimental test results for solid polymer electrolyte materials prepared in examples 1-6
TABLE 2 Experimental test results for assembled cells using POSS-based polyionic liquid solid electrolyte membranes prepared in examples 1-6
TABLE 3 test Rate discharge specific Capacity of assembled batteries utilizing POSS-based polyion liquid solid electrolyte membranes prepared in examples 1-6
As can be seen from tables 1-3, the solid polymer electrolyte material prepared by the above example has good thermal stability, high mechanical strength, high room temperature ionic conductivity, and more ideal electrochemical window and lithium ion transference number. The POSS-based polyion liquid solid electrolyte membrane assembled battery prepared by the embodiment has more advantages of first charge capacity, first coulombic efficiency, 100-cycle charge capacity, 100-cycle discharge capacity, 100-cycle coulombic efficiency and rate discharge specific capacity.
The embodiment relates to a POSS-based polyion liquid solid electrolyte membrane and a preparation method thereof, 1-Vinyl Imidazole Monomer (VIM) is dissolved in toluene or isopropanol, then an initiator is added, stirring is carried out under the protection of nitrogen, reflux reaction is carried out, when white substances are generated, toluene or isopropanol solution of heptaisobutyl methacryloyl POSS Monomer (MAPOSS) is immediately added, after 12h of reaction, suction filtration, washing of toluene or isopropanol and drying are carried out, so as to obtain polymer P [ MAPOSS-VIM ] white solid, quaternary ammonium alkylation reaction is carried out on the polymer P [ MAPOSS-VIM ] [ Br ] and n-bromo-butane to synthesize polyion liquid P [ MAPOSS-VIM ] [ TFSI ] through ion exchange reaction with bis (trifluoromethane sulfonyl imide Lithium (LiTFSI) to obtain yellow solid POSS-based polyion liquid (P [ MAPOSS-VIM ] [ TFSI ]) material. The POSS-based polyionic liquid and PVDF-HFP are dissolved in DMF, lithium salt and ionic liquid are added, the mixture is poured into a polytetrafluoroethylene mold after being uniformly stirred, and vacuum drying is carried out, so that the POSS-based polyionic liquid solid electrolyte membrane can be obtained. The electrolyte has the advantages of high thermal stability, good film forming property, no flammability and no leakage, and can greatly improve the safety performance of the lithium ion battery. Has high ionic conductivity, wide electrochemical window, good compatibility with electrode materials, excellent cyclicity and rate capability, and can be applied to the field of lithium ion batteries.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (9)
1. A preparation method of a POSS-based polyion liquid solid electrolyte material is characterized by comprising the following steps:
(1) synthesis of POSS-based polyion liquid material:
a. adding an initiator into a toluene or isopropanol solution of an N-vinyl imidazole monomer (VIm), stirring under the protection of nitrogen, carrying out reflux reaction at 60-80 ℃, immediately adding a toluene or isopropanol solution of a heptaisobutyl methacryloyl POSS Monomer (MAPOSS) when a white precipitate is generated, continuously reacting for at least 12h, carrying out suction filtration on the product solution, washing for at least 2 times by using toluene or isopropanol, and drying to obtain a polymer P [ MAPOSS-VIm ] white solid;
the mass ratio of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) to the N-vinylimidazole monomer (VIm) is 1:3-1: 10;
the concentration of the toluene or isopropanol solution of the N-vinyl imidazole monomer (VIm) is 2-3 mol/L;
the concentration of the toluene or isopropanol solution of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) is 0.1-0.2 mol/L;
b. dissolving the polymer P [ MAPOSS-VIm ] obtained in the step a in an ethanol solvent to obtain an ethanol solution of the polymer P; calculating the theoretical substance amount of imidazole ring according to the charge ratio of N-vinyl imidazole monomer (VIm) and heptaisobutyl methacryloyl POSS Monomer (MAPOSS), weighing bromoalkane with the amount of 1-2 times of the imidazole ring substance, dripping into the ethanol solution of the polymer P at a speed of not more than 2 drops per second under the conditions of ice water bath and nitrogen protection, after the dropwise addition, the mixed solution is continuously stirred for 4-7 days at room temperature for reaction, when the reaction is finished, partial ethanol solvent is removed by rotary evaporation, ethyl acetate is continuously dropwise added into the obtained product solution until no solid is precipitated, then carrying out suction filtration on the product solution, washing the product solution for at least 2 times by using ethyl acetate, then carrying out vacuum drying on the collected product for at least 24h at the temperature of 60-70 ℃, thus obtaining a light yellow powder solid product P [ MAPOSS-VIm ] [ Br ];
c. dissolving the P [ MAPOSS-VIm ] [ Br ] obtained in the step b in N, N-Dimethylformamide (DMF), weighing lithium bistrifluoromethanesulfonylimide (LiTFSI) with the molar ratio equal to the bromide ion of the P [ MAPOSS-VIm ] [ Br ] and dissolving the lithium bistrifluoromethanesulfonylimide (LiTFSI) in water, dropping the aqueous solution of lithium salt into the DMF solution of the P [ MAPOSS-VIm ] [ Br ] at the speed of no less than two drops per second, and continuously and violently stirring the mixed solution at room temperature for no more than 24 hours to react after the dropping is finished; along with the reaction, a large amount of solid is continuously separated out; after the reaction is finished, carrying out suction filtration on the product solution, washing for at least 2 times by using deionized water, and carrying out vacuum drying for at least 24h at 60-80 ℃ to obtain a faint yellow powdery solid P [ MAPOSS-VIm ] [ TFSI ], so as to obtain a POSS-based polyion liquid material P [ MAPOSS-VIm ] [ TFSI ];
(2) preparation of solid polymer electrolyte material:
2-4.5g of POSS-based polyionic liquid material P [ MAPOSS-VIm ] [ TFSI ] and 1.5-2.0g of poly (vinylidene fluoride-hexafluoropropylene) (P (VDF-HFP)), 0-3g of room temperature ionic liquid and 0.5-2.0g of lithium bistrifluoromethanesulfonylimide (LiTFSI) are dissolved in 5-12ml of DMF or DMSO solvent, stirred at 70-90 ℃, and uniformly mixed to obtain solid polymer electrolyte slurry, the solid polymer electrolyte slurry is poured into a polytetrafluoroethylene mold, defoamed in a vacuum oven at 60-90 ℃, dried for 10-30h, and then the solvent is removed to obtain the solid polymer electrolyte material.
2. The preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1, wherein the POSS-based polyion liquid solid electrolyte material is prepared by the following steps: in the step (1), the initiator is at least one of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisoheptonitrile, azobisdicyclohexylnitrile, benzoyl peroxide, lauroyl peroxide and potassium persulfate.
3. The preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1, wherein the POSS-based polyion liquid solid electrolyte material is prepared by the following steps: in the step (1), the initiator is used in an amount of 0.1 to 1.2% by mass based on the total mass of the N-vinylimidazole monomer (VIm) and the heptaisobutylmethacryloyl POSS Monomer (MAPOSS).
4. The method for producing a POSS-based polyionic liquid solid electrolyte membrane according to claim 1, wherein: in the step (1), the alkyl bromide is at least one of ethyl bromide, n-propyl bromide, n-butyl bromide, pentane bromide and n-hexane bromide.
5. The preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1, wherein the POSS-based polyion liquid solid electrolyte material is prepared by the following steps: in the step (1), reflux reaction is carried out at 65-80 ℃; the mass ratio of the heptaisobutylmethacryloyl POSS Monomer (MAPOSS) to the N-vinylimidazole monomer (VIm) is 1:5-1: 10; the concentration of the toluene or isopropanol solution of the N-vinyl imidazole monomer (VIm) is 2.656-3 mol/L; the concentration of the toluene or isopropanol solution of the heptaisobutyl methacryloyl POSS Monomer (MAPOSS) is 0.14-0.20 mol/L; weighing bromoalkane which is 1.2 to 1.8 times of the amount of imidazole ring substances in the heptaisobutylmethacryloyl POSS Monomer (MAPOSS) and the N-vinyl imidazole monomer (VIm); adding lithium bistrifluoromethanesulfonimide (LiTFSI) and stirring the mixed solution at room temperature for 2-24 h.
6. The preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1, wherein the POSS-based polyion liquid solid electrolyte material is prepared by the following steps: in the step (2), 1-methyl-3-propyl imidazole bis (trifluoromethyl) sulfonyl imide salt or 1-butyl-3-methyl imidazole bis (trifluoromethyl) sulfonyl imide salt is adopted as the room-temperature ionic liquid.
7. The preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1, wherein the POSS-based polyion liquid solid electrolyte material is prepared by the following steps: in the step (2), 2-4g of POSS-based polyionic liquid material P [ MAPOSS-VIm ] [ TFSI ] and 1.5-2.0g of poly (vinylidene fluoride-hexafluoropropylene) (P (VDF-HFP)), 2-3g of room temperature ionic liquid and 1.2-1.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) are dissolved in 10-12ml of DMF or DMSO solvent and stirred uniformly at 80-90 ℃ to obtain solid polymer electrolyte slurry.
8. A POSS-based polyion liquid solid electrolyte membrane is characterized in that: the POSS-based polyion liquid solid electrolyte material is prepared by the preparation method of the POSS-based polyion liquid solid electrolyte material in claim 1.
9. The POSS-based polyionic liquid solid electrolyte membrane as claimed in claim 8 wherein: the preparation method of the POSS-based polyion liquid solid electrolyte material as claimed in claim 1 is adopted to prepare the solid polymer electrolyte material, and the POSS-based polyion liquid solid electrolyte membrane is obtained after slicing by a slicing machine.
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