CN112242554A - Composite solid electrolyte membrane, preparation method thereof and solid battery - Google Patents
Composite solid electrolyte membrane, preparation method thereof and solid battery Download PDFInfo
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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
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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
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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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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Abstract
The application relates to the field of solid batteries, and discloses a composite solid electrolyte membrane, a preparation method thereof and a solid battery. A method for producing a composite solid electrolyte membrane, comprising the steps of: soaking a cured film containing polymer solid electrolyte, silicon dioxide and inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide, and drying to obtain the composite solid electrolyte film; wherein the polymer solid electrolyte is polyvinylidene fluoride-hexafluoropropylene. The composite solid electrolyte membrane obtained by the preparation method provided by the application has the advantage of high ionic conductivity.
Description
Technical Field
The application relates to the field of batteries, in particular to a composite solid electrolyte membrane, a preparation method thereof and a solid battery.
Background
In recent years, the safety accidents caused by organic electrolyte with low boiling point, low flash point, flammability and volatility are increased along with the increase of the application scale of the lithium battery, and the development of the high specific energy lithium secondary battery is greatly restricted. The all-solid-state battery adopting the solid electrolyte to replace the traditional organic liquid electrolyte is expected to fundamentally solve the safety problem of the battery, and is an ideal chemical power supply for electric automobiles and large-scale energy storage equipment. Since the electrolyte membrane in the solid-state battery is in a solid-state form, there is a drawback in lithium ion conduction. In order to obtain good charge and discharge performance of the battery, the ionic conductivity of the solid electrolyte membrane is an important point for improvement.
In terms of solid electrolyte, most polymer solid electrolytes have low room temperature ionic conductivity (10)-5～10-6S cm-1) The practical application of the method is limited. The focus of research and development is a composite electrolyte membrane, such as a nanocomposite solid electrolyte membrane, obtained by combining a polymer electrolyte and an inorganic electrolyte, wherein the electrolyte membrane contains both a polymer electrolyte and a nano inorganic filler (such as an inorganic solid electrolyte filler), and the electrolyte membrane has attracted great interest due to its good processability, flexibility and reasonable ionic conductivity, and the solid electrolyte membrane obtained by pouring the electrolyte membrane on a culture dish has good mechanical properties and high safety. However, in terms of ionic conductivity of the composite solid electrolyte membrane, although the ionic conductivity has been enhanced by doping a filler, blending, copolymerizing, and crosslinking a polymer, the ionic conductivity is still not ideal enough.
Disclosure of Invention
The application discloses a composite solid electrolyte membrane, a preparation method thereof and a solid battery.
In order to achieve the purpose, the application provides the following technical scheme:
a method of making a composite solid electrolyte membrane comprising the steps of:
soaking a cured film containing polymer solid electrolyte, silicon dioxide and inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide, and drying to obtain the composite solid electrolyte film;
wherein the polymer solid electrolyte is polyvinylidene fluoride-hexafluoropropylene.
Further, the mass ratio of the polymer solid electrolyte, the silicon dioxide and the inorganic solid electrolyte is (55-45): (15-5): (30-50).
Further, the preparation method of the cured film comprises the following steps:
dissolving the polymer solid electrolyte, the silicon dioxide and the inorganic solid electrolyte in a solvent, and uniformly mixing to obtain a prefabricated mixture;
and coating the prefabricated mixture on a substrate, and separating after drying to obtain the cured film.
Further, in the preparation of the prefabricated mixture, the magnetic stirring is adopted for mixing, the stirring temperature is 40-50 ℃, and the stirring time is 12-24 h.
Further, the prefabricated mixture is coated on a substrate and then dried, wherein the drying temperature is 25-35 ℃, and the drying time is 40-50 h.
Further, the concentration of the lithium bis (fluorosulfonyl) imide salt in the solution containing the lithium bis (fluorosulfonyl) imide salt is 0.9-1.1 mo/L.
Further, the dipping time of the cured film in the solution is 20-30 h.
A composite solid electrolyte membrane is obtained by the preparation method provided by the application.
Further, the composite solid electrolyte membrane has an ionic conductivity of more than 1 × 10-3S cm-1。
A solid-state battery comprises a positive pole piece, a negative pole piece and a composite solid electrolyte membrane provided by the application and arranged between the positive pole piece and the negative pole piece.
By adopting the technical scheme of the application, the beneficial effects are as follows:
the preparation method of the composite solid electrolyte membrane provided by the application comprises the steps of preparing a solid electrolyte containing a polymer and silicon dioxide SiO2And soaking the solidified film with the inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide. The polymer solid electrolyte in the present application is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). In the curing film used in the preparation method, the polyvinylidene fluoride-hexafluoropropylene has a fiber structure, the curing film can absorb more lithium bis (fluorosulfonyl) imide through a soaking method, and meanwhile, the silicon dioxide in the curing film can reduce the junction of the polyvinylidene fluoride-hexafluoropropyleneCrystallinity disturbs the order of molecular chain segments, thereby improving ion mobility and finally obtaining the composite solid electrolyte membrane with high ionic conductivity.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein as well as preferred features may be combined with each other to form new technical solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percentages by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values. The "range" disclosed herein may be in the form of one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits. In the present application, unless otherwise indicated, the individual reactions or process steps may be performed in sequence, or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. Moreover, any methods or materials similar or equivalent to those described herein can also be used in the present application.
In a first aspect, the present application provides a method of making a composite solid electrolyte membrane, the method comprising the steps of:
soaking a cured film containing polymer solid electrolyte, silicon dioxide and inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide, and drying to obtain the composite solid electrolyte film;
wherein the polymer solid electrolyte is polyvinylidene fluoride-hexafluoropropylene.
The preparation method of the composite solid electrolyte membrane provided by the application comprises the steps of preparing a solid electrolyte containing a polymer and silicon dioxide SiO2And soaking the solidified film with the inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide. The polymer solid electrolyte in the present application is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). In the curing film used in the preparation method, the polyvinylidene fluoride-hexafluoropropylene has a fiber structure, the curing film can absorb more lithium bis (fluorosulfonyl) imide through a soaking method, and meanwhile, the silicon dioxide in the curing film can reduce the crystallinity of the polyvinylidene fluoride-hexafluoropropylene and disturb the orderliness of molecular chain segments of the polyvinylidene fluoride-hexafluoropropylene, so that the ion mobility is improved, and the composite solid electrolyte film with high ion conductivity is finally obtained.
In the solidified membrane, polyvinylidene fluoride-hexafluoropropylene and silicon dioxide are used as an electrolyte framework, an inorganic solid electrolyte is used as a fast ion conductor and is doped into the electrolyte framework, the solidified membrane of a lithium ion channel is constructed together, and the ionic conductivity of the composite solid electrolyte membrane can be effectively improved.
Among them, the inorganic solid electrolyte may be, for example, LAGP, LATP, or the like.
In one embodiment of the present application, the mass ratio of the polymer solid electrolyte, the silica, and the inorganic solid electrolyte is (55-45): (15-5): (30-50).
The stability and ionic conductivity of the composite solid electrolyte membrane can be further improved by defining the mass ratio of the polymer solid electrolyte, silica and inorganic solid electrolyte.
Wherein, in the cured film, the mass ratio of the polymer solid electrolyte, the silicon dioxide and the inorganic solid electrolyte may be 55:15:30, 50:15:30, 45:15:30, 55:10:30, 55:5:30, 55:15:40, 55:15:45, 55:15:50, 55:15:40, 50:15:40, 45:15:40, 55:15:50, 50:15:50, 45:15: 50. It is to be understood that the above-mentioned mass ratio is merely an illustrative example, and the mass ratio of the polymer solid electrolyte, the silica, and the inorganic solid electrolyte in the present application includes, but is not limited to, the above-mentioned ratio.
In one embodiment of the present application, the method for preparing the cured film comprises the steps of: dissolving the polymer solid electrolyte, the silicon dioxide and the inorganic solid electrolyte in a solvent, and uniformly mixing to obtain a prefabricated mixture; and coating the prefabricated mixture on a substrate, and separating after drying to obtain the cured film.
Wherein, the solvent is a volatile organic solvent, including but not limited to acetone, N-methyl pyrrolidone.
In one embodiment of the present application, the preformed mixture is prepared by mixing with magnetic stirring at a temperature of 40-50 deg.C for a period of 12-24 hours.
Through magnetic stirring, raw materials such as polyvinylidene fluoride-hexafluoropropylene and silicon dioxide can be in full contact, agglomeration is reduced, the uniformity of a framework structure is improved, and the uniformity of dispersion of inorganic solid electrolyte in the framework structure is improved.
The stirring temperature in magnetic stirring is typically but not exclusively 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃ or 50 ℃, and the stirring time is typically but not exclusively 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
In one embodiment of the present application, the pre-mixture is coated on a substrate and then dried at a temperature of 25-35 ℃ for a period of 40-50 hours. Wherein, the drying temperature is typically but not limited to, for example, 25 ℃, 27 ℃, 29 ℃, 30 ℃, 32 ℃ or 35 ℃, and the drying time is typically but not limited to, for example, 40h, 42h, 44h, 46h, 48h or 50 h.
In one embodiment of the present application, the concentration of lithium bis (fluorosulfonyl) imide salt in the solution containing the lithium bis (fluorosulfonyl) imide salt is 0.9-1.1 mo/L. By optimizing the concentration of the lithium bis (fluorosulfonyl) imide salt in the solution, the adsorption amount of the cured film on the lithium bis (fluorosulfonyl) imide salt can be increased, so that the conductivity of the composite solid electrolyte film is increased. Wherein, the concentration of the lithium bis (fluorosulfonyl) imide salt can be typically but not limitatively, for example, 0.9mo/L, 0.95mo/L, 1.0mo/L, 1.05mo/L or 1.1 mo/L.
Among these, in the solution containing lithium bis (fluorosulfonyl) imide salt, the solvent may be tetraethylene glycol dimethyl ether (TEGDME), for example.
In one embodiment of the present application, the dipping time of the cured film in the solution is 20 to 30 hours. The dipping time of the cured film in the solution can be, for example, 20h, 22h, 24h, 26h, 28h or 30h, typically but not limitatively.
In a second aspect, the present application provides a composite solid electrolyte membrane prepared using the method of the first aspect of the present application.
Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and silicon dioxide (SiO) are mixed by using the composite solid electrolyte membrane obtained by the preparation method2) As an electrolyte framework, a fast ion conductor inorganic solid electrolyte is doped to construct a composite electrolyte with a lithium ion channel, and after the composite electrolyte is poured into a film, the cured film is soaked in a solvation ionic liquid LiFSI solution, so that the ionic conductivity of the composite electrolyte is further improved. Polyvinylidene fluoride-hexafluoropropylene has a fiber structure, more solvated ionic liquid can be adsorbed by a soaking method, silicon dioxide can reduce the crystallinity of a polymer, the order of molecular chain segments is disordered, the ion migration rate after lithium salt is added later is improved, and finally, the composite solid electrolyte membrane which is high in ionic conductivity and beneficial to the stability of a lithium cathode is obtained.
The composite solid electrolyte membrane is applied to the all-solid-state lithium secondary battery, and the obtained battery has the advantages of stable interface and small impedance.
In addition, the first and second substrates are,the prepared composite solid electrolyte membrane has ultrahigh room-temperature ionic conductivity which is more than 1 x 10 by introducing silicon dioxide and treating by a soaking method-3S cm-1High transference number of lithium ion and wide electrochemical window.
In a third aspect, the present application provides a solid-state battery, including a positive electrode plate, a negative electrode plate, and a composite solid electrolyte membrane interposed between the positive electrode plate and the negative electrode plate.
The positive pole piece comprises a positive current collector and a positive material layer coated on the surface of the positive current collector. The positive electrode active material in the positive electrode material layer may be, for example, lithium cobaltate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, or the like. The negative electrode pole piece comprises a negative electrode current collector and a negative electrode material layer coated on the surface of the negative electrode current collector, and a negative electrode active material in the negative electrode material layer can be a carbon material. In the button cell, the negative electrode plate can also be a lithium plate.
The composite solid electrolyte membrane of the present application will be described in further detail with reference to examples and comparative examples.
Example 1
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11), weighing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and silicon dioxide (SiO) in a mass ratio of 55:15:302) Adding the mixture with LAGP into a single-neck round-bottom flask containing acetone solvent, and magnetically stirring and mixing at 45 ℃ for 12 hours to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Example 2
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11) weighing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the mass ratio of 50:10:40,Silicon dioxide (SiO)2) Adding the mixture with LAGP into a single-neck round-bottom flask containing acetone solvent, and magnetically stirring and mixing at 45 ℃ for 12 hours to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Example 3
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11), weighing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and silicon dioxide (SiO) in a mass ratio of 45:5:502) Adding the mixture with LAGP into a single-neck round-bottom flask containing acetone solvent, and magnetically stirring and mixing at 45 ℃ for 12 hours to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Comparative example 1
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11), weighing a mixture of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and LAGP (LAGP) in a mass ratio of 55:45, adding the mixture into a single-neck round-bottom flask containing an acetone solvent, and magnetically stirring and mixing the mixture for 12 hours at 45 ℃ to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Comparative example 2
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11), weighing a mixture of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and LAGP (LAGP) in a mass ratio of 50:50, adding the mixture into a single-neck round-bottom flask containing an acetone solvent, and magnetically stirring and mixing the mixture for 12 hours at 45 ℃ to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Comparative example 3
Preparation of a composite solid electrolyte membrane comprising the steps of:
step S11), weighing a mixture of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and LAGP (LAGP) in a mass ratio of 45:55, adding the mixture into a single-neck round-bottom flask containing an acetone solvent, and magnetically stirring and mixing the mixture for 12 hours at 45 ℃ to obtain a prefabricated mixture;
step S12), coating the obtained prefabricated mixture on a polytetrafluoroethylene template, and then carrying out vacuum drying for 48 hours at the temperature of 30 ℃ to obtain a cured film;
step S13) soaking the cured film in 1mol/L LiFSI-TEGDME solvated ionic liquid for 24h to obtain the composite solid electrolyte film.
Solid-state batteries were assembled using the composite solid electrolyte membranes provided in examples 1 to 3 and comparative examples 1 to 3, respectively, and the cycle stability and capacity of the solid-state batteries were tested. The test results are shown in Table 1.
The preparation process of the solid-state battery is as follows:
the prepared positive pole piece (LCO/Li)2.3-xC0.7+xB0.3-xO3/LAGP) and the composite solid electrolyte membrane are hot-pressed together to obtain the anode/electrolyte layer composite sheet, wherein the hot-pressing pressure is 1MPa, and the hot-pressing temperature is 80-100 ℃; cutting the positive electrode/electrolyte layer composite sheet obtained after hot pressing into a wafer with the diameter of 16 mm; sequentially stacking the battery shell, the positive electrode/electrolyte layer composite sheet, the Li sheet, the gasket, the spring sheet and the battery shell,then placing the button cell on a punch for punching to obtain the button cell, and then preheating the button cell for 12 hours at the temperature of 60-80 ℃. Wherein, the surface of the Li sheet is polished to remove an oxide layer on the surface of the Li sheet. The battery is subjected to a charge-discharge test at 0.05C, and the electrochemical properties are measured as follows:
| serial number | Initial capacity of battery | Circulate for 50 circles | Capacity retention rate |
| Example 1 | 144.6mAh/g | 143.2mAh/g | 99.0％ |
| Example 2 | 142.2mAh/g | 139.6mAh/g | 98.2％ |
| Example 3 | 140.5mAh/g | 137.1mAh/g | 97.6％ |
| Comparative example 1 | 139.2mAh/g | 133.8mAh/g | 96.1％ |
| Comparative example 2 | 138.6mAh/g | 132.2mAh/g | 95.4％ |
| Comparative example 3 | 137.5mAh/g | 129.7mAh/g | 94.3％ |
As can be seen from the data in table 1, the cycle performance of the batteries obtained by using the technical solutions of the examples of the present application is significantly better than that of the batteries of comparative examples 1 to 3.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
Claims (10)
1. A method for producing a composite solid electrolyte membrane, characterized by comprising the steps of:
soaking a cured film containing polymer solid electrolyte, silicon dioxide and inorganic solid electrolyte in a solution containing lithium bis (fluorosulfonyl) imide, and drying to obtain the composite solid electrolyte film;
wherein the polymer solid electrolyte is polyvinylidene fluoride-hexafluoropropylene.
2. The production method according to claim 1, wherein the mass ratio of the polymer solid electrolyte, the silica, and the inorganic solid electrolyte is (55-45): (15-5): (30-50).
3. The production method according to claim 1, characterized in that the production method of the cured film comprises the steps of:
dissolving the polymer solid electrolyte, the silicon dioxide and the inorganic solid electrolyte in a solvent, and uniformly mixing to obtain a prefabricated mixture;
and coating the prefabricated mixture on a substrate, and separating after drying to obtain the cured film.
4. The method according to claim 3, wherein the pre-prepared mixture is prepared by mixing by magnetic stirring at 40-50 ℃ for 12-24 hours.
5. The method according to claim 3, wherein the pre-mixture is dried after being coated on the substrate at a temperature of 25 to 35 ℃ for 40 to 50 hours.
6. The method according to any one of claims 1 to 5, wherein the concentration of lithium bis (fluorosulfonyl) imide salt in the solution containing the lithium bis (fluorosulfonyl) imide salt is 0.9 to 1.1 mo/L.
7. The production method according to any one of claims 1 to 5, wherein the dipping time of the cured film in the solution is 20 to 30 hours.
8. A composite solid electrolyte membrane obtained by the production method according to any one of claims 1 to 7.
9. The composite solid electrolyte membrane according to claim 8, characterized in that the ionic conductivity of the composite solid electrolyte membrane is greater than 1 x 10-3S cm-1。
10. A solid-state battery comprising a positive electrode tab, a negative electrode tab, and the composite solid electrolyte membrane according to claim 8 or 9 interposed between the positive electrode tab and the negative electrode tab.
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Application publication date: 20210119 |