CN114725506A - Sodium ion composite polymer solid electrolyte and preparation method thereof - Google Patents
Sodium ion composite polymer solid electrolyte and preparation method thereof Download PDFInfo
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- CN114725506A CN114725506A CN202210495018.8A CN202210495018A CN114725506A CN 114725506 A CN114725506 A CN 114725506A CN 202210495018 A CN202210495018 A CN 202210495018A CN 114725506 A CN114725506 A CN 114725506A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 156
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 139
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 65
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000000945 filler Substances 0.000 claims abstract description 38
- 159000000000 sodium salts Chemical class 0.000 claims description 52
- 239000003960 organic solvent Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 47
- 239000012528 membrane Substances 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 38
- 239000001856 Ethyl cellulose Substances 0.000 claims description 36
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 36
- 229920001249 ethyl cellulose Polymers 0.000 claims description 36
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 30
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000002228 NASICON Substances 0.000 claims description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 11
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 229920002678 cellulose Polymers 0.000 abstract description 10
- 239000001913 cellulose Substances 0.000 abstract description 10
- 239000005518 polymer electrolyte Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 67
- 239000011259 mixed solution Substances 0.000 description 33
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 10
- 239000011149 active material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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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
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Abstract
The invention discloses a sodium ion composite polymer solid electrolyte and a preparation method thereof, and relates to the technical field of high polymer materials and new energy materials. According to the sodium ion composite polymer solid electrolyte, the active filler is added into the cellulose-based gel polymer electrolyte, so that the ionic conductivity and the electrochemical performance of the composite polymer solid electrolyte are improved, and the composite polymer solid electrolyte with high ionic conductivity, flexibility, light weight, high mechanical strength and adhesiveness is obtained; the invention also discloses a preparation method of the all-solid-state sodium ion battery, which optimizes the cycle life and electrochemical performance of the all-solid-state sodium ion battery using the composite polymer solid electrolyte and realizes the all-solid-state of the sodium ion battery.
Description
Technical Field
The invention relates to a sodium ion composite polymer solid electrolyte and a preparation method thereof, and relates to the technical field of high polymer materials and new energy materials.
Background
Rechargeable batteries are one of the cornerstones of green energy transformation and will play a key role in decarburization and electrification of global economy. Efficient, sustainable and safe batteries have great potential in reducing the consumption of natural resources and environmental pollution caused by fossil fuels, and thus their development will promote the shift to the circular economy model.
The sodium ion battery is a feasible substitute of the ubiquitous lithium ion battery, and reenters the field of sustainable energy storage. Compared with the lithium ion battery, the sodium ion battery has lower influence on global warming, fossil consumption, fresh water eutrophication and the like. The sodium is rich in nature (the sodium content in the earth crust is 2.36 percent) and low in price, and the stability in a full discharge state obviously improves the safety of the memory device. And the organic electrolyte has flammability and leakage risk, and brings great potential safety hazard to the battery. Sodium has a higher reactivity than lithium, and safety is more important for sodium ion batteries. The solid electrolyte with flame retardance, non-volatility and no leakage can effectively improve the safety. In addition, all-solid-state sodium ion batteries based on solid-state electrolytes have several major advantages: 1) high safety; 2) a scalable electrochemical window; 3) high energy density. Therefore, the development of all-solid-state sodium ion batteries not only has wide application prospect, but also is enough to cause revolutionary changes of energy storage devices and applications, and has very important effect on national energy safety strategy.
In recent years, portable flexible electronic devices have gained wide attention as an important direction for the development of smart wearable fields. At present, liquid electrolyte is mostly adopted as the electrolyte of a power supply, but the problems of easy corrosion, easy leakage, easy volatilization and the like generally exist, extra high-cost packaging is needed, and the further popularization and application of the liquid electrolyte in the field of flexible electronic devices are limited.
Currently, many scientific and technical challenges are still faced in developing a solid-state sodium ion battery with superior performance, for example: lower ionic conductivity, greater interfacial (electrode/solid electrolyte) impedance, electrode material volume change, low loading of electrode active material, and poor cycling stability, among others. At present, liquid electrolyte is mostly adopted as the electrolyte of a power supply, but the problems of easy corrosion, easy leakage, easy volatilization and the like generally exist, extra high-cost packaging is needed, and the further popularization and application of the liquid electrolyte in the field of flexible electronic devices are limited. Therefore, a flexible solid electrolyte with high ionic conductivity, wide electrochemical potential window, good mechanical strength and good cycling stability is needed as a substitute. The key point for overcoming the challenge is whether a novel composite polymer solid electrolyte can be prepared, and the ionic conductivity, the mechanical strength and the solid-solid interface compatibility are improved.
Disclosure of Invention
The invention aims to provide a sodium ion composite polymer solid electrolyte and a preparation method thereof, and the sodium ion composite polymer solid electrolyte improves the ionic conductivity and electrochemical performance of the composite polymer solid electrolyte by adding an active filler into a cellulose-based gel polymer electrolyte, so as to obtain the composite polymer solid electrolyte with high ionic conductivity, flexibility, light weight, high mechanical strength and adhesiveness; the invention also discloses a preparation method of the all-solid-state sodium ion battery, which optimizes the cycle life and electrochemical performance of the all-solid-state sodium ion battery using the composite polymer solid electrolyte and realizes the all-solid state of the sodium ion battery.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of a sodium ion composite polymer solid electrolyte comprises the following steps:
s1: precursor solution preparation
Dissolving a polymer in an organic solvent through magnetic stirring, adding ethyl cellulose, stirring again until the solution becomes a transparent solution, adding sodium salt and active filler into the transparent solution, and obtaining a precursor solution through magnetic stirring;
s2: preparation of composite polymer solid electrolyte
And injecting the precursor solution into a preset mold, drying to remove the organic solvent and form the composite polymer solid electrolyte membrane, taking out the composite polymer solid electrolyte membrane from the preset mold, and drying to obtain the sodium ion composite polymer solid electrolyte membrane.
Further, the polymer is dissolved in the organic solvent in an amount of 30-80 wt.% of the organic solvent, and the time for dissolving the polymer in the organic solvent completely is 1-24 h by magnetic stirring.
Further, the polymer comprises at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol (PEG);
the organic solvent comprises one or more of acetone, N-Dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone (NMP).
Further, the addition amount of the ethyl cellulose is 1-50 wt.% of the organic solvent.
Further, sodium salt is added into the transparent solution in a concentration range of 0.5-2mol/L and an addition amount of 0.5-20 vol.%, wherein the sodium salt is obtained by mixing one or more of sodium perchlorate, sodium hexafluorophosphate and sodium bistrifluoromethylsulfonyl imide sodium salt with one or more of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate;
the active filler is NASICON, and the adding amount is 0.5-40 wt.% of the organic solvent.
Further, adding sodium salt and active filler into the transparent solution, and stirring by magnetic force to obtain the precursor solution within the time range of 1-24 h; the stirring speed range is 100-1600 r/min;
further, the preparation of the composite polymer solid electrolyte comprises:
pouring the prepared precursor solution into a preset mold, and putting the mold into a vacuum drying oven; the range of the preset temperature in the vacuum drying oven is 40-100 ℃, and the range of the preset time is 12-48 h.
Further, the thickness of the composite polymer solid electrolyte membrane is 50-100 μm.
Another object of the present invention is to provide a sodium ion composite polymer solid electrolyte, including the sodium ion composite polymer solid electrolyte membrane prepared by the above preparation method.
The invention has the beneficial effects that:
according to the sodium ion composite polymer solid electrolyte and the preparation method thereof, the active filler is added into the cellulose base gel polymer electrolyte, so that the ionic conductivity and the electrochemical performance of the composite polymer solid electrolyte are improved, and the composite polymer solid electrolyte with high ionic conductivity, flexibility, light weight, high mechanical strength and adhesiveness is obtained; the invention also discloses a preparation method of the all-solid-state sodium ion battery, which optimizes the cycle life and electrochemical performance of the all-solid-state sodium ion battery using the composite polymer solid electrolyte and realizes the all-solid state of the sodium ion battery.
Compared with the prior art, the preparation method of the sodium ion composite polymer solid electrolyte adopts the mixed solution of the polymer and the organic solvent in which the ethyl cellulose is dissolved, so that the obtained composite polymer solid electrolyte forms a compact structure, and the agglomeration of the nano active filler is relieved. Sodium salt is added, so that the interface of the gel polymer electrolyte has better stability and electrochemical performance; the sodium ion transport number is greatly increased compared to known electrolytes;
according to the preparation method, the renewable gel polymer electrolyte provides a new direction for the design and environmental protection of the composite polymer electrolyte; in addition, the process flow of the preparation of the precursor solution and the preparation of the composite polymer solid electrolyte is simple, the complex reaction process is not involved basically, and the energy consumption and the equipment investment are reduced; in addition, the ethyl cellulose is a reproducible environment-friendly polymer, and three wastes are not generated basically in any process link, so that the method accords with the concept of green industry and is environment-friendly.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is a flow chart illustrating a method for preparing a sodium ion composite polymer solid electrolyte according to an embodiment of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a cellulose-based composite polymer solid electrolyte added with an active filler obtained in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern (XRD) of a cellulose-based composite polymer solid electrolyte with an added active filler obtained in example 1 of the present invention;
FIG. 4 is a comparative graph showing the cycles of a symmetrical battery (Na/composite polymer solid electrolyte/Na) using a cellulose-based composite polymer solid electrolyte added with an active filler obtained in example 1 of the present invention.
FIG. 5 is a graph comparing Electrochemical Impedance Spectroscopy (EIS) of a cellulose-based composite polymer solid electrolyte added with an active filler obtained in example 1 of the present invention.
FIG. 6 is a diagram showing the cycle of a symmetrical cell (Na/composite polymer solid electrolyte/Na) of cellulose-based composite polymer solid electrolyte added with an active filler obtained in example 2 of the present invention.
FIG. 7 is an Electrochemical Impedance Spectrum (EIS) of a cellulose-based composite polymer solid electrolyte with added active fillers obtained in example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
A preparation method of a sodium ion composite polymer solid electrolyte comprises the following steps:
s1: precursor solution preparation
Dissolving a polymer in an organic solvent through magnetic stirring, adding ethyl cellulose, stirring again until the solution becomes a transparent solution, adding sodium salt and active filler into the transparent solution, and obtaining a precursor solution through magnetic stirring;
s2: preparation of composite polymer solid electrolyte
And injecting the precursor solution into a preset mold, drying to remove the organic solvent and form the composite polymer solid electrolyte membrane, taking out the composite polymer solid electrolyte membrane from the preset mold, and drying to obtain the sodium ion composite polymer solid electrolyte membrane.
In the step of preparing the precursor solution, presetting sodium salt, presetting sodium electrolyte concentration and first preset time in the preparation process; the preparation method of the solution comprises the steps of preparing a solution by adopting a preset sodium salt, a preset sodium salt concentration and a first preset time, wherein the preset sodium salt is obtained by mixing one or more of sodium perchlorate, sodium hexafluorophosphate and sodium bistrifluoromethylsulfonyl imide sodium salt with one or more of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate solvents, the sodium salt concentration is the concentration of the sodium salt in the solvents, the concentration range is 0.5-2mol/L, the first preset time is the time for completely dissolving a polymer in an organic solvent by magnetic stirring, and the first preset time range is 1-24 hours. Specifically, the preparation process adopts the preset sodium salt, the preset sodium electrolyte concentration and the first preset time, so that the composite polymer electrolyte forms a compact structure, and the retention capacity of the organic liquid electrolyte is greatly improved.
The preset proportion is the mass proportion of the polymer, the sodium salt and the organic solvent, and the mass proportion ranges from 30 wt.% to 80 wt.%. Specifically, according to the preset proportion, the flexibility of the composite polymer solid electrolyte can be improved, the polymer crystallization can be effectively inhibited, the glass transition temperature can be reduced, better mechanical property and ionic conductivity can be presented, the finally obtained composite polymer solid electrolyte membrane has higher mechanical property and ionic conductivity, and the battery has better cycle performance.
The polymer includes at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol (PEG). Specifically, the composite solid electrolyte membrane obtained finally has excellent ionic conductivity, mechanical properties and electrochemical properties due to the advantages of good electrochemical stability, high dielectric constant, good thermodynamic stability, a structure beneficial to rapid ion migration and the like.
The solvent comprises one or two of acetone, N-Dimethylformamide (DMF), acetonitrile and N-methylpyrrolidone (NMP). Specifically, the solvent has good compatibility with the polymer, and the finally obtained composite polymer solid electrolyte membrane has a better microstructure and mechanical properties.
Dissolving the certain amount of polymer in a proper amount of organic solvent, and magnetically stirring until the polymer is completely dissolved in the organic solvent; weighing ethyl cellulose according to a predetermined proportion, and stirring the solution of the ethyl cellulose and the polymer which are completely dissolved in the organic solvent again until the solution becomes transparent; and weighing a certain amount of sodium salt and active filler, adding into the transparent solution, and magnetically stirring to obtain a mixed solution.
The magnetic stirring is carried out at a preset stirring rotating speed, and the range of the preset stirring rotating speed is 100-1600 r/min; and adding the sodium salt into the transparent solution of the polymer completely dissolved in the organic solvent, and stirring by magnetic force to obtain the mixed solution for a second preset time, wherein the second preset time is 1-24 hours. Specifically, by adopting the magnetic stirring at the rotating speed and for the time, the polymer, the ethyl cellulose and the sodium salt can be dissolved in the organic solvent more uniformly, the generated bubbles are reduced, and the structure is further uniform and compact, so that the composite polymer solid electrolyte has smaller impedance, longer cycle performance, chemical stability and more excellent electrochemical performance.
The step of pouring the mixed solution into a preset mold, and then drying to remove the organic solvent and form the composite polymer solid electrolyte membrane comprises: pouring the mixed solution into the preset mold, putting the preset mold into a vacuum drying oven, adjusting the temperature in the vacuum drying oven to a preset temperature, and keeping the preset temperature for a third preset time to obtain the composite solid electrolyte membrane; the third preset time ranges from 12h to 48 h; the preset temperature range is 40-100 ℃.
According to the sodium ion composite polymer solid electrolyte and the preparation method thereof, ethyl cellulose is adopted to prepare a precursor solution, and the precursor solution is poured into a film, so that the obtained composite polymer solid electrolyte forms a compact structure, and the dispersibility of the active filler is improved. The solid-solid interface compatibility of the electrolyte is enhanced, the electrochemical performance is good, and the transference number of sodium ions is greatly increased. And the cycle life of the solid-state battery using the composite solid electrolyte membrane is prolonged, and the performance is excellent. Specifically, the third predetermined time and the preset temperature range can also be used for enabling the finally obtained activated composite polymer solid electrolyte membrane to have a better microstructure and mechanical properties.
The thickness of the composite solid electrolyte membrane after the rolling treatment is 50-100 μm, so that the composite solid electrolyte membrane after the activation has better performance, such as better sodium ion transmission performance and better battery cycle performance.
The invention is illustrated below with reference to specific examples:
the examples of the invention are based on the active filler prepared, which is NASICON. The embodiment of the invention adds NASICON active filler, lowers the glass transition temperature of the polymer and promotes the decomposition of sodium salt. In the embodiment of the invention, based on the prepared composite polymer solid electrolyte precursor solution, the composite polymer solid electrolyte precursor solution is an ethyl cellulose base composite polymer solid electrolyte precursor solution. According to the embodiment of the invention, the precursor solution is prepared by using ethyl cellulose, so that the obtained composite polymer solid electrolyte forms a compact structure, and the uniform distribution of active fillers is promoted. The flexibility of the sodium ion composite polymer solid electrolyte is enhanced, the solid-solid interface contact and compatibility of an electrode/solid electrolyte interface are improved, the electrochemical performance is good, and the transference number of sodium ions is greatly increased. The concentration of ionized sodium ions of the composite polymer solid electrolyte is improved, the uniform deposition of sodium metal is promoted, the stability of the all-solid-state sodium ion battery is improved, and the cycle life of the all-solid-state sodium ion battery is prolonged.
Specifically, as shown in fig. 1, the preparation method of the active filler-added composite polymer solid electrolyte precursor solution provided by the invention comprises the following steps:
a preparation method of a sodium ion composite polymer solid electrolyte comprises the following steps:
s1: precursor solution preparation
Dissolving a polymer in an organic solvent through magnetic stirring, adding ethyl cellulose, stirring again until the solution becomes a transparent solution, adding sodium salt and active filler into the transparent solution, and obtaining a precursor solution through magnetic stirring;
s2: preparation of composite polymer solid electrolyte
And injecting the precursor solution into a preset mold, drying to remove the organic solvent and form the composite polymer solid electrolyte membrane, taking out the composite polymer solid electrolyte membrane from the preset mold and drying to obtain the sodium ion composite polymer solid electrolyte membrane.
The preparation method of the composite polymer solid electrolyte provided by the invention can be briefly summarized as follows:
the polymer, ethyl cellulose, organic solvent, sodium salt and active filler are stirred by magnetic force according to the proportion to form transparent mixed solution.
And obtaining the sodium ion composite polymer solid electrolyte membrane by using the mixed solution.
Among them, it is understood that the step of forming the transparent mixed solution by magnetically stirring the polymer, the ethylcellulose, the organic solvent, the sodium salt and the active filler in proportion may include a specific step of preparing the precursor solution specifically shown in fig. 1. The step of obtaining the composite polymer solid electrolyte membrane using the mixed solution may include the step of preparing the composite polymer solid electrolyte shown in fig. 1, which will not be described herein again.
Specifically, the composite polymer solid electrolyte membrane may have a thickness of 30 to 100 μm; it can be understood that in the sodium ion composite polymer solid electrolyte and the preparation method thereof, ethyl cellulose is adopted to prepare a precursor solution, and the precursor solution is poured into a film, so that the obtained composite polymer solid electrolyte forms a compact structure, and the uniform distribution of the active filler is promoted. The flexibility of the sodium ion composite polymer solid electrolyte is enhanced, the solid-solid interface contact and compatibility of an electrode/solid electrolyte interface are improved, the electrochemical performance is good, and the transference number of sodium ions is greatly increased. And the cycle life of the solid-state battery using the composite solid electrolyte membrane is prolonged, and the performance is excellent. In addition, the thickness of the composite polymer solid electrolyte membrane is 30-100 μm, so that the composite polymer solid electrolyte membrane added with the sodium salt and the active filler has better performance, such as better flexibility and better battery cycle performance. Furthermore, the sodium ion composite polymer solid electrolyte and the preparation method thereof have simple process flow, basically do not relate to complex reaction processes, and reduce the energy consumption and the investment of equipment. In addition, the ethyl cellulose is a reproducible environment-friendly polymer, and three wastes are not generated basically in any process link, so that the method accords with the concept of green industry and is environment-friendly.
Example 1
(1) Preparing a precursor solution: weighing PEO according to the proportion of 30 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 1 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 0.5 wt.% of NASICON active filler and 0.5 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 1mol/L, the stirring time is 24h, and the rotating speed is 800 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 80 ℃ for 24 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 50 microns.
In the example, the cellulose-based composite polymer solid electrolyte added with the active filler is subjected to physical and electrochemical tests, and as can be seen from a scanning electron microscope in fig. 2, the composite polymer solid electrolyte has a compact surface and the NASICON powder is uniformly distributed. As can be seen from fig. 3, the composite polymer solid electrolyte has a broadened diffraction peak and a reduced crystallinity, confirming a reduction in the glass transition temperature of the composite polymer solid electrolyte. From fig. 4 and fig. 5, the sodium metal symmetric battery based on the composite polymer solid electrolyte has a small polarization voltage of 0.16V, can stably circulate for more than 1200 cycles, and is fitted with an equivalent circuit diagram to show that the bulk impedance is 12 Ω.
Example 2
(1) Preparing a precursor solution: weighing PEO according to the proportion of 40 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 10 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 40 wt.% of NASICON active filler and 10 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.8mol/L, the stirring time is 12h, and the rotating speed is 1000 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 100 ℃ for 12 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 100 microns.
In the present example, as shown in fig. 6, the sodium metal symmetric battery (Na/composite polymer solid electrolyte/Na) based on the composite polymer solid electrolyte can stably cycle for more than 600h and has a stable polarization voltage of 0.17V.
Example 3
(1) Preparing a precursor solution: weighing PEO according to the proportion of 50 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 10 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 10 wt.% of NASICON active filler and 20 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.7mol/L, the stirring time is 8h, and the rotating speed is 1600 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 60 ℃ for 20 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 60 microns.
In this example, an alternating current impedance test was performed on the composite polymer solid electrolyte, as shown in fig. 7, based on the composite polymer solid electrolyte, the composite polymer solid electrolyte has a significant advantage of low impedance, and the bulk impedance is 13 Ω.
Example 4
(1) Preparing a precursor solution: weighing PEO according to the proportion of 60 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 20 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 10 wt.% of NASICON active filler and 15 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.4mol/L, the stirring time is 10h, and the rotating speed is 1000 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 100 ℃ for 12 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 100 microns.
The composite polymer solid electrolyte of the present example was tested physically and electrochemically, and had relatively low impedance and polarization, as well as long cycle life.
Example 5
(1) Preparing a precursor solution: weighing PEO according to the proportion of 70 wt.% and dissolving the PEO in acetonitrile solution for stirring, adding 5 wt.% of ethyl cellulose after the PEO is completely dissolved, continuously stirring until the solution is transparent, and then adding 5 wt.% of ethyl cellulose
Continuously stirring NASICON active filler and 20 vol.% sodium salt, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.8mol/L, the stirring time is 24h, and the rotating speed is 800 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 80 ℃ for 24 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 50 microns.
The composite polymer solid electrolyte is subjected to physical and electrochemical tests, and has relatively low impedance and polarization and long cycle life.
Example 6
(1) Preparing a precursor solution: weighing PEO according to the proportion of 80 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 5 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 1 wt.% of NASICON active filler and 20 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.5mol/L, the stirring time is 12h, and the rotating speed is 1600 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 60 microns.
The composite polymer solid electrolyte of the present example was tested physically and electrochemically, and had relatively low impedance and polarization, as well as long cycle life.
Example 7
(1) Preparing a precursor solution: weighing PEO according to the proportion of 40 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 50 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 1 wt.% of NASICON active filler and 20 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.6mol/L, the stirring time is 8h, and the rotating speed is 800 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 100 ℃ for 24 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 100 microns.
The composite polymer solid electrolyte of the present example was tested physically and electrochemically, and had relatively low impedance and polarization, as well as long cycle life.
Example 8
(1) Preparing a precursor solution: weighing PEO according to the proportion of 30 wt.% and dissolving the PEO in acetonitrile solution and stirring, adding 50 wt.% of ethyl cellulose after the PEO is completely dissolved and continuously stirring until the solution is transparent, then adding 3 wt.% of NASICON active filler and 20 vol.% of sodium salt and continuously stirring, wherein the sodium salt is a mixed solution of sodium perchlorate, dimethyl carbonate and ethyl methyl carbonate, the concentration is 0.8mol/L, the stirring time is 24h, and the rotating speed is 1000 r/min; to obtain a mixed solution of the polymer, the organic solvent, the ethyl cellulose, the sodium salt and the active material which are completely and uniformly dissolved.
(2) Preparation of composite polymer solid electrolyte: and (2) slowly pouring the mixed solution obtained in the step (1) into a polytetrafluoroethylene mold, and standing the polytetrafluoroethylene mold in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to remove the organic solvent to obtain the composite solid electrolyte membrane with the thickness of 60 microns.
The composite polymer solid electrolyte of the present example was tested physically and electrochemically, and had relatively low impedance and polarization, as well as long cycle life.
In the sodium ion composite polymer solid electrolyte and the preparation method thereof, ethyl cellulose is adopted to prepare a precursor solution, and the precursor solution is poured to form a film, so that the obtained composite polymer solid electrolyte forms a compact structure, and the uniform distribution of active fillers is promoted. The flexibility of the sodium ion composite polymer solid electrolyte is enhanced, the solid-solid interface contact and compatibility of an electrode/solid electrolyte interface are improved, the electrochemical performance is good, and the transference number of sodium ions is greatly increased. And the cycle life of the solid-state battery using the composite solid electrolyte membrane is prolonged, and the performance is excellent. In addition, the thickness of the composite polymer solid electrolyte membrane is 30-100 μm, so that the composite polymer solid electrolyte membrane added with the sodium salt and the active filler has better performance, such as better flexibility and better battery cycle performance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A preparation method of a sodium ion composite polymer solid electrolyte is characterized by comprising the following steps:
s1: precursor solution preparation
Dissolving a polymer in an organic solvent through magnetic stirring, adding ethyl cellulose, stirring again until the solution becomes a transparent solution, adding sodium salt and active filler into the transparent solution, and obtaining a precursor solution through magnetic stirring;
s2: preparation of composite polymer solid electrolyte
And injecting the precursor solution into a preset mold, drying to remove the organic solvent and form the composite polymer solid electrolyte membrane, taking out the composite polymer solid electrolyte membrane from the preset mold, and drying to obtain the sodium ion composite polymer solid electrolyte membrane.
2. The method for producing a sodium ion composite polymer solid electrolyte according to claim 1, wherein: the polymer is dissolved in the organic solvent according to 30-80 wt.% of the organic solvent, and the time for completely dissolving the polymer in the organic solvent by magnetic stirring is 1-24 h.
3. The method for producing a sodium ion composite polymer solid electrolyte according to claim 2, characterized in that: the polymer comprises at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol (PEG);
the organic solvent comprises one or more of acetone, N-Dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone (NMP).
4. The method for producing a sodium ion composite polymer solid electrolyte according to claim 1, wherein: the addition amount of the ethyl cellulose is 1-50 wt% of the organic solvent.
5. The method for producing a sodium ion composite polymer solid electrolyte according to claim 1, characterized in that: adding sodium salt into the transparent solution, wherein the concentration range of the sodium salt is 0.5-2mol/L, and the addition amount is 0.5-20 vol.%, and the sodium salt is obtained by mixing one or more of sodium perchlorate, sodium hexafluorophosphate and sodium bistrifluoromethylsulfonyl imide sodium salt with one or more of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate solvents;
the active filler is NASICON, and the adding amount is 0.5-40 wt.% of the organic solvent.
6. The method for producing a sodium ion composite polymer solid electrolyte according to claim 5, wherein: adding sodium salt and active filler into the transparent solution, and stirring by magnetic force to obtain the precursor solution within the time range of 1-24 h; the stirring speed range is 100-1600 r/min.
7. The method for producing a sodium ion composite polymer solid electrolyte according to claim 1, wherein: the preparation of the composite polymer solid electrolyte comprises the following steps:
pouring the prepared precursor solution into a preset mold, and putting the mold into a vacuum drying oven; the range of the preset temperature in the vacuum drying oven is 40-100 ℃, and the range of the preset time is 12-48 h.
8. The method for producing a sodium ion composite polymer solid electrolyte according to claim 7, wherein: the thickness of the composite polymer solid electrolyte membrane is 50-100 mu m.
9. A sodium ion composite polymer solid electrolyte is characterized in that: the sodium ion composite polymer solid electrolyte is prepared by the preparation method of the sodium ion composite polymer solid electrolyte according to any one of claims 1 to 8.
10. An application of a sodium ion composite polymer solid electrolyte prepared by a preparation method of the sodium ion composite polymer solid electrolyte in an all-solid-state sodium ion battery.
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