CN110034330B - Preparation method of composite solid electrolyte for lithium/sodium battery - Google Patents
Preparation method of composite solid electrolyte for lithium/sodium battery Download PDFInfo
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- CN110034330B CN110034330B CN201910284401.7A CN201910284401A CN110034330B CN 110034330 B CN110034330 B CN 110034330B CN 201910284401 A CN201910284401 A CN 201910284401A CN 110034330 B CN110034330 B CN 110034330B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a composite solid electrolyte for a lithium/sodium ion battery. The preparation method comprises the steps of dispersing aramid fibers in an organic solvent to obtain a high-dispersity aramid nanofiber solution, adding lithium/sodium salt and a polymer matrix material, stirring and dispersing, and then obtaining the lithium/sodium ion composite polymer solid electrolyte film through casting or coating and drying processes. The method is simple to operate and low in cost, and the obtained electrolyte has the advantages of high ionic conductivity, wide electrochemical window, good mechanical and thermal stability, inhibition of growth of metal dendrites and the like. The composite solid electrolyte has wide application prospect in lithium/sodium ion batteries.
Description
Technical Field
The invention belongs to the technical field of solid lithium/sodium batteries, and relates to a preparation method of a lithium/sodium ion composite solid electrolyte.
Background
The lithium/sodium ion battery has the advantages of high energy density, long cycle life, no memory effect, no pollution and the like, is widely applied to the fields of portable electronic products, transportation, large-scale energy storage and the like, but the use of the liquid electrolyte easily causes safety problems of liquid leakage, gas expansion, combustion, explosion and the like.
The polymer solid electrolyte which has the characteristics of simple preparation, low price, good film forming property and flexibility, low interface impedance between the polymer solid electrolyte and an electrode is adopted as the electrolyte and the diaphragm of the lithium/sodium ion battery, so that the safety problem caused by the liquid electrolyte is expected to be fundamentally solved, the application possibility of lithium/sodium metal negative electrodes, high-voltage positive electrodes and convertible positive electrode materials such as oxygen, sulfur and the like can be provided, the energy density of the battery is obviously improved, and the polymer solid electrolyte has a great development space in the aspects of widening the working temperature range of the battery, prolonging the service life of the battery, simplifying the manufacturing process of the battery and the like. However, the polymer matrix in the polymer electrolyte has higher crystallinity and lower dissociation degree of lithium/sodium salt, so that the room temperature conductivity of the electrolyte is lower. In addition, the polymer electrolyte has the defects of narrow electrochemical window, low mechanical strength, easy penetration of lithium/sodium metal dendrites into an electrolyte membrane and the like, and the application of the polymer electrolyte in a solid lithium/sodium battery is seriously hindered.
At present, inorganic nano particles are often used as filling materials to prepare composite polymer solid electrolytes of inorganic/organic hybrid systems, but the problems of nano particle agglomeration, high polymer matrix crystallinity and the like exist, the ionic conductivity, mechanical strength and other properties of the polymer electrolytes are improved slightly, and the application requirements of solid lithium/sodium ion batteries cannot be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a composite polymer solid electrolyte, which can obviously improve the ionic conductivity, the mechanical strength and other properties of the polymer electrolyte and improve the properties of a solid lithium/sodium ion battery.
In order to achieve the purpose, the invention adopts aramid fiber as a modified material to prepare the aramid fiber/polymer matrix/lithium (sodium) salt composite solid electrolyte, and the specific technical scheme is as follows:
1) preparing a certain amount of aramid fiber and inorganic salt (such as potassium hydroxide and sodium hydroxide) in dimethyl sulfoxide, stirring for a period of time at a certain temperature to prepare an aramid nanofiber solution with good dispersibility, and then performing dialysis treatment to obtain an aramid nanofiber/dimethyl sulfoxide solution with high purity and good dispersibility; the aramid fiber is one or two of poly-p-phenylene terephthamide and poly-m-phenylene isophthalamide.
2) Adding a certain amount of the aramid nano-fiber solution into an organic solvent, continuously stirring for a period of time to completely disperse the solution, adding lithium/sodium salt and a polymer matrix material, and continuously stirring at a certain temperature to obtain an aramid nano-fiber/polymer matrix material/lithium (sodium) salt composite solution with good dispersibility; the polymer matrix material is one or more of polyethylene oxide, polyacrylonitrile, polycarbonate, polymethyl methacrylate, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene, the lithium salt comprises one or more of lithium chloride, lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide and lithium trifluoromethylsulfonyl imide, the sodium salt comprises one or more of sodium chloride, sodium perchlorate, sodium hexafluorophosphate, bistrifluoromethylsulfonyl imide and sodium trifluoromethylsulfonyl imide, and the organic solvent is one or more of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
3) Treating the composite solution by a slurry coating method or a solution casting method, and drying the obtained composite gel film to obtain an aramid nano-fiber/polymer matrix/lithium (sodium) salt composite solid electrolyte film with a certain thickness; the content of the aramid fiber in the composite solid electrolyte is 0.1-40.0 wt%, and the content of the lithium/sodium salt in the composite solid electrolyte is 5.0-50.0 wt%.
The invention provides a lithium/sodium ion composite solid electrolyte and a preparation method thereof. The method has the advantages of simple preparation, low cost and the like, and the obtained solid electrolyte film has high ionic conductivity (more than or equal to 0.1mS/cm at room temperature), good mechanical and thermal stability (the mechanical tensile strength is more than or equal to 2.5MPa), and can effectively inhibit the growth of lithium/sodium metal dendrites. The composite solid electrolyte film prepared by the invention can meet the use requirements of lithium/sodium ion batteries, and the cycle performance and safety of the batteries are obviously improved.
Drawings
Fig. 1 is an optical photograph of a composite polymer solid electrolyte film.
Fig. 2 is an SEM photograph of a composite polymer solid electrolyte thin film.
Fig. 3 is a graph showing the change of ion conductivity with temperature of a composite polymer solid electrolyte film.
Fig. 4 is a mechanical tensile stress-strain curve of a composite polymer solid electrolyte membrane.
Fig. 5 is a thermogravimetric plot of a composite polymer solid electrolyte membrane.
Detailed Description
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
The first embodiment is as follows:
step 1: weighing 2.0g of aramid fiber and 1.0g of potassium hydroxide, putting the aramid fiber and the potassium hydroxide into a certain amount of dimethyl sulfoxide, stirring for 7 days at normal temperature (or stirring for 3 days at 60 ℃) to completely dissolve the aramid fiber, putting the aramid fiber solution into a dialysis bag, and stirring for 2 hours in the dimethyl sulfoxide to obtain an aramid nanofiber solution with high purity and good dispersibility, wherein the concentration of the aramid nanofiber is about 12.5 mg/mL;
step 2: taking 10mL of the aramid nano-fiber solution, adding 36mL of dimethylformamide, continuously stirring for 1h, then respectively adding 1.835g of polyethylene oxide and 0.665g of lithium perchlorate, and continuously stirring for 12h at 40 ℃ to obtain a composite solution with good dispersibility;
and step 3: and pouring the composite solution into a polytetrafluoroethylene culture dish, drying at 60 ℃ for 24 hours until the solvent is completely evaporated, and continuously drying at 60 ℃ for 24 hours in vacuum to obtain the composite solid electrolyte film with the aramid nanofiber content of about 5 wt%.
Claims (7)
1. A lithium/sodium ion composite polymer solid electrolyte is characterized in that: the electrolyte consists of aramid nano-fibers, a polymer matrix material and lithium/sodium salt;
the preparation method of the composite polymer solid electrolyte comprises the following steps:
1) preparing a certain amount of aramid fiber and potassium hydroxide or sodium hydroxide in dimethyl sulfoxide, stirring for a period of time at a certain temperature to prepare an aramid nanofiber solution with good dispersibility, and then performing dialysis treatment to obtain an aramid nanofiber/dimethyl sulfoxide solution with high purity and good dispersibility;
2) adding a certain amount of the aramid nano-fiber solution into an organic solvent, continuously stirring for a period of time to completely disperse the solution, adding lithium/sodium salt and a polymer matrix material, and continuously stirring at a certain temperature to obtain an aramid nano-fiber/polymer matrix material/lithium salt composite solution or an aramid nano-fiber/polymer matrix material/sodium salt composite solution with good dispersibility;
3) treating the composite solution by a slurry coating method or a solution casting method, and drying the obtained composite gel film to obtain an aramid nanofiber/polymer matrix/lithium salt composite solid electrolyte film or an aramid nanofiber/polymer matrix/sodium salt composite solid electrolyte film with a certain thickness;
the content of the aramid fiber in the composite solid electrolyte is 0.1-40.0 wt%; the average diameter of the aramid fiber is 2.0-2000.0 nm; the content of the lithium/sodium salt in the composite solid electrolyte is 5.0-50.0 wt%; the polymer matrix material is polyethylene oxide.
2. The method for producing a composite polymer solid electrolyte according to claim 1, characterized by comprising the steps of:
1) preparing a certain amount of aramid fiber and potassium hydroxide or sodium hydroxide in dimethyl sulfoxide, stirring for a period of time at a certain temperature to prepare an aramid nanofiber solution with good dispersibility, and then performing dialysis treatment to obtain an aramid nanofiber/dimethyl sulfoxide solution with high purity and good dispersibility;
2) adding a certain amount of the aramid nano-fiber solution into an organic solvent, continuously stirring for a period of time to completely disperse the solution, adding lithium/sodium salt and a polymer matrix material, and continuously stirring at a certain temperature to obtain an aramid nano-fiber/polymer matrix material/lithium salt composite solution or an aramid nano-fiber/polymer matrix material/sodium salt composite solution with good dispersibility;
3) and treating the composite solution by a slurry coating method or a solution casting method, and drying the obtained composite gel film to obtain the aramid nano-fiber/polymer matrix/lithium salt composite solid electrolyte film or the aramid nano-fiber/polymer matrix/sodium salt composite solid electrolyte film with a certain thickness.
3. The composite solid-state electrolyte of claim 1, wherein: the aramid fiber is one or two of poly-p-phenylene terephthamide and poly-m-phenylene isophthalamide.
4. The composite solid-state electrolyte of claim 1, wherein: the lithium salt comprises one or more of lithium chloride, lithium perchlorate, lithium hexafluorophosphate, lithium bis (trifluoromethyl) sulfonyl imide and lithium trifluoromethyl sulfonyl imide.
5. The composite solid-state electrolyte of claim 1, wherein: the sodium salt comprises one or more of sodium chloride, sodium perchlorate, sodium hexafluorophosphate, sodium bistrifluoromethylsulfonyl imide and sodium trifluoromethylsulfonyl imide.
6. The method for producing a composite solid electrolyte according to claim 2, characterized in that: the dialysis treatment in the step 1 is mainly aimed at the preparation of the lithium ion composite solid electrolyte, and the dialysis time is less than or equal to 72 h; the sodium ion composite solid electrolyte prepared from the aramid fiber solution treated by sodium hydroxide can be prepared without dialysis treatment.
7. The method for producing a composite solid electrolyte according to claim 2, characterized in that: the organic solvent in the step 2 is one or more of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
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| CN110592807B (en) * | 2019-09-18 | 2021-05-14 | 宁波大学 | Thin film material for inhibiting growth of lithium dendrite and preparation method thereof |
| CN113506909B (en) * | 2021-05-07 | 2022-07-26 | 鹏盛国能(深圳)新能源集团有限公司 | Lithium battery and electrolyte thereof |
| CN114006032B (en) * | 2021-09-17 | 2024-01-26 | 佛山(华南)新材料研究院 | Solid polymer electrolyte membrane and manufacturing method thereof |
| CN114566713B (en) * | 2022-03-08 | 2023-09-29 | 中国矿业大学 | Electrolyte, preparation method thereof and method for preparing sodium ion battery by using electrolyte |
| CN116666738B (en) * | 2023-08-02 | 2023-09-29 | 河北科技大学 | Solid electrolyte for sodium ion battery and preparation method thereof |
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| CN108242563A (en) * | 2017-12-20 | 2018-07-03 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding alkyl tin groups, alkyl silane groups lithium battery polymer dielectric, preparation method and its application in solid lithium battery |
| CN108417890A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of solid polyelectrolyte material, solid electrolyte membrane and preparation method thereof |
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| CN105811002A (en) * | 2016-03-16 | 2016-07-27 | 中国科学院青岛生物能源与过程研究所 | Organic and inorganic composite all-solid-state electrolyte and all-solid-state battery formed from same |
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| CN108242563A (en) * | 2017-12-20 | 2018-07-03 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding alkyl tin groups, alkyl silane groups lithium battery polymer dielectric, preparation method and its application in solid lithium battery |
| CN108417890A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of solid polyelectrolyte material, solid electrolyte membrane and preparation method thereof |
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