CN118040038A - Polymer electrolyte, preparation method thereof and battery - Google Patents
Polymer electrolyte, preparation method thereof and battery Download PDFInfo
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- CN118040038A CN118040038A CN202410413133.5A CN202410413133A CN118040038A CN 118040038 A CN118040038 A CN 118040038A CN 202410413133 A CN202410413133 A CN 202410413133A CN 118040038 A CN118040038 A CN 118040038A
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- polyvinylidene fluoride
- polymer electrolyte
- lithium salt
- lithium
- triethoxysilane
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- 239000005518 polymer electrolyte Substances 0.000 title claims description 48
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002033 PVDF binder Substances 0.000 claims abstract description 87
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 87
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 48
- 159000000002 lithium salts Chemical class 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- 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 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 229910018557 Si O Inorganic materials 0.000 abstract description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005796 dehydrofluorination reaction Methods 0.000 abstract description 7
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 description 18
- 239000007784 solid electrolyte Substances 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/0566—Liquid materials
-
- 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
- H01M2300/0088—Composites
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to the low-temperature application field of polymer-based solid lithium metal batteries, which greatly reduces the Tg of polyvinylidene fluoride PVDF by introducing Si-O bond into the polyvinylidene fluoride PVDF chain by utilizing (2-cyanoethyl) triethoxysilane TEOSCN, thereby enhancing the ability of Li+ conduction along the polymer chain. Meanwhile, the high-concentration-C (identical to N) group can inhibit damage to an electrode caused by PVDF dehydrofluorination, so that the low-temperature-resistant high-stability lithium metal solid-state battery is realized.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a polymer electrolyte, a preparation method thereof and a battery.
Background
The flammability of the commercial organic liquid electrolyte itself, as well as the incompatibility with the lithium metal anode, leaves a great safety hazard for the proper operation of the battery. Practical application of lithium metal batteries is affected by uncontrolled exothermic reactions between the active metal lithium and the organic liquid electrolyte. A safer and more reliable solid electrolyte is certainly a better alternative to traditional commercial liquid electrolytes. The rechargeable solid-state battery consisting of the solid-state electrolyte and the lithium metal anode has a great application prospect in a battery system for improving the energy density and the high safety, and is expected to break the bottleneck for limiting the development of the most advanced lithium ion battery.
The wettability of the inorganic solid electrolyte to the electrode is poor, resulting in ion transport being limited by incompatibility of the electrolyte solid particles with the electrode interface. The polymer solid electrolyte has the advantages of good interface wettability of liquid electrolyte and high safety of inorganic solid electrolyte, and can ensure long-term safe operation of the battery. But in which the polyvinylidene fluoride PVDF-based electrolyte has greater rigidity at a lower temperature, the ion-conducting ability is weak, resulting in rapid degradation of the battery capacity with a decrease in temperature. The severe dehydrofluorination reaction in polyvinylidene fluoride PVDF-based polymer solid state electrolytes greatly reduces the useful life of the polymer solid state battery.
Disclosure of Invention
The invention discloses a polymer electrolyte, a preparation method thereof and a battery, which are used for solving the problems of poor battery cycle performance caused by weak ion conduction capability and polymer decomposition reaction of polyvinylidene fluoride PVDF-based polymer solid electrolyte in the prior art.
In order to achieve the above object, the embodiment of the present specification adopts the following technical solutions:
in a first aspect, there is provided a polymer electrolyte comprising: (2-cyanoethyl) triethoxysilane, polyvinylidene fluoride and lithium salts.
Optionally, the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride is 1:1 to 1:3.
Optionally, the lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiFSI and lithium trifluoromethanesulfonate LiCF 3SO3.
Optionally, the polymer electrolyte is solid or liquid;
when the polymer electrolyte is a liquid, the polymer electrolyte further comprises a solvent, wherein the solvent is one or more of N-methylpyrrolidone NMP, N-dimethylformamide DMF, and N, N-dimethylacetamide DMAc.
In a second aspect, there is provided a method of preparing a polymer electrolyte comprising the steps of:
(2-cyanoethyl) triethoxysilane is added to a lithium salt solution containing polyvinylidene fluoride to obtain a polymer electrolyte.
Optionally, adding (2-cyanoethyl) triethoxysilane into a lithium salt solution containing polyvinylidene fluoride, stirring at room temperature for 3-6 h, and then continuing stirring at 60-80 ℃ for 24-48 h to obtain the polymer electrolyte.
Optionally, the preparation method of the lithium salt solution containing polyvinylidene fluoride comprises the following steps:
Dispersing polyvinylidene fluoride in a solvent to obtain a mixed solution;
and adding lithium salt into the mixed solution to obtain a lithium salt solution containing polyvinylidene fluoride.
Optionally, the mass ratio of the polyvinylidene fluoride to the solvent is 1:7-1:9.
Optionally, the solvent is one or more of N-methylpyrrolidone NMP, N-dimethylformamide DMF, N-dimethylacetamide DMAc.
Optionally, the mass ratio of the polyvinylidene fluoride to the lithium salt is 2-6: 1.
In a third aspect, there is provided a battery comprising the polymer electrolyte of the first aspect or the polymer electrolyte prepared by the preparation method of the second aspect.
The above at least one technical scheme adopted by the embodiment of the application can achieve the following beneficial effects:
The invention relates to the low-temperature application field of polymer-based solid lithium metal batteries, which greatly reduces the Tg of polyvinylidene fluoride PVDF by introducing Si-O bond into the polyvinylidene fluoride PVDF chain by utilizing (2-cyanoethyl) triethoxysilane TEOSCN, thereby enhancing the ability of Li+ conduction along the polymer chain. Meanwhile, the high-concentration-C (identical to N) group can inhibit damage to an electrode caused by PVDF dehydrofluorination, so that the low-temperature-resistant high-stability lithium metal solid-state battery is realized.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
FIG. 1 is a graph showing the cycle performance of the lithium-ion battery of example 1 of the present invention at low temperature of-20deg.C, 0.2mA/0.2 mAh;
FIG. 2 is a graph showing the cycle performance of the lithium sulfur full cell of example 1 of the present invention at a low temperature of-20℃and 0.2 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below with reference to specific embodiments of the present application and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
According to an embodiment of the present application, there is provided a polymer electrolyte including: (2-cyanoethyl) triethoxysilane, polyvinylidene fluoride and lithium salts.
The Si-O bond in the (2-cyanoethyl) triethoxysilane TEOSCN greatly reduces the Tg of the PVDF, thereby enhancing the low temperature resistance of the solid electrolyte. Meanwhile, the high-concentration Si-O groups can act with acidic byproducts in the electrolyte, so that corrosion of the electrolyte to the anode is avoided, and the cycling stability of the anode is improved. The lowest electrostatic potential region of the-C.ident.N group in the molecule favors the dissociation of the lithium salt. Pi-pi coupling of the-C [ identical to ] N group improves the oxidation stability of the polymer matrix, inhibits the damage of PVDF dehydrofluorination to the electrode, and ensures the long cycle performance of the lithium metal battery. The introduction of TEOSCN, which contains both Si-O bonds and-C.ident.N groups, ultimately renders the PVDF electrolyte dual-functional with respect to resistance to low temperatures and corrosion.
In the examples of the present specification, the (2-cyanoethyl) triethoxysilane and the polyvinylidene fluoride may be mixed in any ratio, and the present invention is not limited thereto. Optionally, the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride is 1:1 to 1:3.
In the embodiments of the present disclosure, the lithium salt may be any one or more reagents, so long as the electrolyte is capable of conducting lithium ions, which the present invention is not limited to. Optionally, the lithium salt in the lithium salt solution containing polyvinylidene fluoride is lithium bis (trifluoromethanesulfonyl) imide LiTFSI, and one or more of lithium bis (fluorosulfonyl) imide LiSSI and lithium trifluoromethanesulfonate LiCF 3SO3 are mixed.
In the embodiments of the present specification, the polymer electrolyte is solid or liquid. When the polymer electrolyte is a liquid, the polymer electrolyte further includes a solvent, which may be selected from any one or more reagents, as long as it is capable of dissolving (2-cyanoethyl) triethoxysilane, polyvinylidene fluoride, and a lithium salt, which is not limited in the present invention. Optionally, the solvent in the lithium salt solution containing polyvinylidene fluoride is one or more of N-methyl pyrrolidone NMP, N-dimethylformamide DMF and N, N-dimethylacetamide DMAc.
According to an embodiment of the present application, there is provided a method for preparing a polymer electrolyte, including the steps of:
Adding (2-cyanoethyl) triethoxysilane into a lithium salt solution containing polyvinylidene fluoride, stirring, and heating and stirring to obtain the polymer electrolyte.
In the examples of the present specification, the stirring time and stirring temperature are not limited in the present invention, and a mixing effect may be achieved. Optionally, adding (2-cyanoethyl) triethoxysilane into the lithium salt solution containing polyvinylidene fluoride, stirring for 3-6 hours at room temperature, and then continuously stirring for 24-48 hours at 60-80 ℃ to obtain the polymer electrolyte.
In the embodiment of the specification, the preparation method of the lithium salt solution containing polyvinylidene fluoride comprises the following steps:
Dispersing polyvinylidene fluoride in a solvent to obtain a mixed solution;
and adding lithium salt into the mixed solution to obtain a lithium salt solution containing polyvinylidene fluoride.
In the examples of the present specification, the polyvinylidene fluoride and the solvent may be mixed in any ratio, and the present invention is not limited thereto. Optionally, the mass ratio of the polyvinylidene fluoride to the solvent is 1:7-1:9. The stirring time for dispersing the polyvinylidene fluoride in the solvent can be selected to be 24-48 hours.
In the examples of the present specification, the polyvinylidene fluoride and the lithium salt may be mixed in any ratio, and the present invention is not limited thereto. Optionally, the mass ratio of the polyvinylidene fluoride to the lithium salt is 2-6: 1. the stirring time for adding the lithium salt to the mixed solution may be selected to be 24 to 48 hours.
According to an embodiment of the present application, there is provided a battery including the above-mentioned polymer electrolyte or the polymer electrolyte prepared above. Namely, the application of the polymer electrolyte to the lithium symmetric battery and the lithium sulfur battery is provided.
The obtained battery is applied to base station environments with low temperatures in mountain areas, high terrains and the like, the low-temperature capacity, service life and safety stability of the battery can be improved, and the cost of manual maintenance, risk protection and the like is reduced.
Compared with other solid electrolytes, the polymer electrolyte can form better interface contact with the electrode due to the soft characteristic of the polymer electrolyte, and is beneficial to ion conduction. By adding a liquid component into the polymer, not only the wettability of the polymer electrolyte to the electrode can be enhanced, but also the physicochemical properties of the electrolyte can be regulated. The (2-cyanoethyl) triethoxysilane TEOSCN carrying silicon-based functional groups introduces various functional groups into the polymer solid electrolyte, reduces the Tg of the polymer electrolyte, improves the oxidation stability of the electrolyte, and slows down the damage of the polymer to the electrode by dehydrofluorination, thereby ensuring the long cycle characteristic of the lithium metal battery. The introduction of the (2-cyanoethyl) triethoxysilane component with lower Tg and polyvinylidene fluoride for polar interaction can not only reduce the Tg of the material, but also improve the stability of electrolyte due to the silicon-based functional group carried by TEOSCN, and finally realize the low-temperature-resistant and high-stability quasi-solid polymer lithium metal battery.
The invention adopts PVDF-based electrolyte, which can alleviate the safety problem of lithium metal batteries caused by using flammable liquid electrolyte. The (2-cyanoethyl) triethoxysilane is introduced into the electrolyte, so that the damage of the PVDF-based electrolyte to the stability of the electrolyte and the electrode caused by dehydrofluorination can be relieved. The PVDF-based electrolyte modified by the (2-cyanoethyl) triethoxysilane can reduce the low temperature tolerance range of the quasi-solid state battery and enhance the cycling stability of the battery.
According to the invention, PVDF is directly adopted as a polymer matrix, and (2-cyanoethyl) triethoxysilane is introduced in a liquid molecular form in a targeted manner, so that the expansion of a PVDF chain is promoted through the interaction of Si-O bond and C-F polarity, the flexibility of chain segments is increased, and the formation of a crystallization area is prevented, thereby reducing the Tg of the material, and ensuring that the material can still maintain higher mobility at a lower temperature. The (2-cyanoethyl) triethoxysilane needs to be uniformly dissolved in NMP, and then is fully contacted with the molecular chain of PVDF in the form of liquid molecules, so that the polar interaction of Si-O bond and C-F bond on the microscopic level can be realized, the expansion of PVDF chain is promoted, the formation of crystallization area is prevented, and the lithium ion conduction at low temperature is promoted. In addition, the high-concentration Si-O groups fully contacted with the PVDF chain can remove acidic substances formed in the electrolyte, and pi-pi coupling of the-C (identical to N) groups improves the oxidation stability of a polymer matrix, inhibits the damage of PVDF dehydrofluorination to electrodes, and ensures the long cycle performance of the lithium metal battery at a lower temperature.
The following describes in detail the technical solutions provided by the embodiments of the present application with reference to the accompanying drawings.
Example 1:
there is provided a method for preparing a polymer electrolyte, comprising the steps of:
(1) Uniformly dispersing 1.5g of polyvinylidene fluoride in an NMP solvent, uniformly stirring and mixing at a rotating speed of 250rpm for 24 hours to obtain a mixed solution, wherein the mass ratio of the polyvinylidene fluoride to the solvent is 1:7;
(2) The mass ratio of the polyvinylidene fluoride to the lithium salt is 4:1, adding lithium salt into the mixed solution, and continuously stirring for 24 hours to obtain a lithium salt solution containing polyvinylidene fluoride;
(3) Adding (2-cyanoethyl) triethoxysilane into a lithium salt solution containing polyvinylidene fluoride, stirring for 3 hours at room temperature, and then continuing stirring for 24 hours at 80 ℃ to obtain a polymer electrolyte, wherein the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride in the lithium salt solution containing polyvinylidene fluoride is 1:3.
Example 2:
there is provided a method for preparing a polymer electrolyte, comprising the steps of:
(1) Uniformly dispersing 1.5g of polyvinylidene fluoride in an NMP solvent, uniformly stirring and mixing at a rotating speed of 250rpm for 36 hours to obtain a mixed solution, wherein the mass ratio of the polyvinylidene fluoride to the solvent is 1:9;
(2) The mass ratio of the polyvinylidene fluoride to the lithium salt is 2:1, adding lithium salt into the mixed solution, and continuously stirring for 36 hours to obtain a lithium salt solution containing polyvinylidene fluoride;
(3) Adding (2-cyanoethyl) triethoxysilane into a lithium salt solution containing polyvinylidene fluoride, stirring for 6 hours at room temperature, and then continuing stirring for 36 hours at 70 ℃ to obtain a polymer electrolyte, wherein the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride in the lithium salt solution containing polyvinylidene fluoride is 1:1.
Example 3:
there is provided a method for preparing a polymer electrolyte, comprising the steps of:
(1) Uniformly dispersing polyvinylidene fluoride in an NMP solvent, and uniformly stirring and mixing at a rotating speed of 250rpm for 48 hours to obtain a mixed solution, wherein the mass ratio of the polyvinylidene fluoride to the solvent is 1:8;
(2) The mass ratio of the polyvinylidene fluoride to the lithium salt is 6:1, adding lithium salt into the mixed solution, and continuously stirring for 48 hours to obtain a lithium salt solution containing polyvinylidene fluoride;
(3) Adding (2-cyanoethyl) triethoxysilane into a lithium salt solution containing polyvinylidene fluoride, stirring for 4 hours at room temperature, and then continuing stirring for 48 hours at 60 ℃ to obtain a polymer electrolyte, wherein the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride in the lithium salt solution containing polyvinylidene fluoride is 1:2.
Comparative example 1:
there is provided a method for preparing a polymer electrolyte, comprising the steps of:
(1) Uniformly dispersing 1.5g of polyvinylidene fluoride in an NMP solvent, uniformly stirring and mixing at a rotating speed of 250rpm for 24 hours to obtain a mixed solution, wherein the mass ratio of the polyvinylidene fluoride to the solvent is 1:7;
(2) The mass ratio of the polyvinylidene fluoride to the lithium salt is 4:1, adding the lithium salt into the mixed solution, and continuously stirring for 24 hours to obtain the polymer electrolyte.
The polymer electrolytes obtained in examples 1 to 3 and comparative example 1 were uniformly blade-coated on the surface of a clean glass plate, then vacuum-dried at 60℃and tableted to obtain an electrolyte, wherein the blade-coated thickness was 500 nm and the thickness after drying was about 100. Mu.m. The resulting electrolyte was used to assemble lithium symmetric batteries and lithium sulfur batteries.
The lithium-symmetric batteries obtained in examples 1 to 3 and comparative example 1 were cycled at a low temperature of-20℃for a cycle time of 2 hours each and a steady cycle time of 800 hours at 0.2mA/0.2 mAh. The lithium sulfur full cells obtained in examples 1 to 3 and comparative example 1 were cycled at a low temperature of-20℃at 0.2C, leaving a capacity of 500mAh/g after 115 cycles.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (10)
1. A polymer electrolyte, comprising: (2-cyanoethyl) triethoxysilane, polyvinylidene fluoride and lithium salts.
2. The polymer electrolyte according to claim 1, wherein the mass ratio of the (2-cyanoethyl) triethoxysilane to the polyvinylidene fluoride is 1:1 to 1:3.
3. The polymer electrolyte of claim 1 wherein the lithium salt is one or more of lithium bis (triflate) LiTFSI, lithium bis (triflate) LiFSI, lithium triflate LiCF 3SO3.
4. The polymer electrolyte of claim 1, wherein the polymer electrolyte is a solid or a liquid;
when the polymer electrolyte is a liquid, the polymer electrolyte further comprises a solvent, wherein the solvent is one or more of N-methylpyrrolidone NMP, N-dimethylformamide DMF, and N, N-dimethylacetamide DMAc.
5. A method for preparing a polymer electrolyte, comprising the steps of:
(2-cyanoethyl) triethoxysilane is added to a lithium salt solution containing polyvinylidene fluoride to obtain a polymer electrolyte.
6. The method according to claim 5, wherein the polymer electrolyte is obtained by adding (2-cyanoethyl) triethoxysilane to a lithium salt solution containing polyvinylidene fluoride, stirring at room temperature for 3 to 6 hours, and continuing stirring at 60 to 80 ℃ for 24 to 48 hours.
7. The method according to claim 5, wherein the method for preparing a lithium salt solution containing polyvinylidene fluoride comprises the steps of:
Dispersing polyvinylidene fluoride in a solvent to obtain a mixed solution;
and adding lithium salt into the mixed solution to obtain a lithium salt solution containing polyvinylidene fluoride.
8. The preparation method according to claim 7, wherein the mass ratio of the polyvinylidene fluoride to the solvent is 1:7-1:9; and/or the number of the groups of groups,
The solvent is one or more of N-methylpyrrolidone NMP, N-dimethylformamide DMF and N, N-dimethylacetamide DMAc.
9. The preparation method of claim 7, wherein the mass ratio of the polyvinylidene fluoride to the lithium salt is 2-6: 1.
10. A battery characterized in that it comprises the polymer electrolyte according to any one of claims 1 to 4 or the polymer electrolyte produced according to the production method of any one of claims 5 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410413133.5A CN118040038A (en) | 2024-04-07 | 2024-04-07 | Polymer electrolyte, preparation method thereof and battery |
Applications Claiming Priority (1)
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