CN113437359A - Preparation method of polypropylene oxide polymer solid electrolyte film - Google Patents
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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
- H01M10/056—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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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a polypropylene oxide polymer solid electrolyte film, which comprises the following steps: (1) dissolving a polypropylene oxide precursor, an inorganic filler and a lithium salt in an organic solvent, uniformly stirring and mixing, adding an initiator, and stirring for reaction to obtain a mixed slurry; (2) and preparing a wet film by using the mixed slurry, and drying to obtain the solid electrolyte film. Compared with the existing polypropylene oxide solid electrolyte, the polypropylene oxide polymer solid electrolyte film provided by the invention has higher electrochemical performance and mechanical performance.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation method of a solid electrolyte film.
Background
The performance of solid-state batteries is influenced by various aspects of the electrolyte membrane, electrodes, electrode/electrolyte interface, assembly processes, etc., and solid-state electrolytes are of great importance. Polymer solid electrolytes are currently the most promising technology for industrial applications due to their good processability, excellent electrochemical properties and relatively low production cost compared to oxide and sulfide electrolytes. High room temperature ionic conductivity, potential window and ion migration number, and strong mechanical property and chemical stability are the key points for promoting the development of polymer solid electrolyte.
The polypropylene oxide (PPO) system has certain viscoelasticity, higher mechanical strength and good electrochemical performance, and has good prospect when being applied to a solid lithium ion battery. However, there are some drawbacks in the solutions reported in the literature. For example, the electrolyte membrane prepared by adopting a monomer cross-linking method is too thick in the Stanford project group of Stanford university, and the thickness is as high as 200-; the film is hard at normal temperature, which is not beneficial to the interface combination of the solid electrolyte thin film battery; lithium salt is not mixed and added into the electrolyte solution, and the electrolyte membrane cannot be ensured to be completely permeated though the electrolyte solution is soaked in the later period; in the process of assembling the battery, after the electrolyte membrane bubble PC solution is soaked, the swelling is serious, the deformation and the curling are easy to occur, the experiment operation is difficult, and the like. Zhang Ning doctor of Qingdao science and technology university reports a silicon methoxy polypropylene oxide electrolyte, which is prepared by dissolving silicon methoxy polypropylene oxide and LiBOB lithium salt in acetonitrile solution, adding alumina or plastic crystal succinonitrile, blade-coating to form a film and then drying at 60 ℃. The reported silicon methoxy polypropylene oxide electrolyte has excellent performance, but acetonitrile with strong corrosivity is adopted in the preparation process, a large amount of succinonitrile is added, the drying temperature is only 60 ℃, and the prepared electrolyte is actually a gel electrolyte, so that the mechanical property of the electrolyte is weak; only single LiBOB lithium salt and alumina filler with low content (about 15%) are used in the preparation process, and optimization promotion of ionic conductivity and thermodynamic performance of the film is limited. Goodenough et al have attempted to prepare 50% LLZO fillersThe filled polyethylene oxide electrolyte shows better thermal property, but the mechanical property of the formed film is poorer due to the defects of the preparation method and the selected system, and the room-temperature ionic conductivity is only 10-5S/cm。
Therefore, the exploration of a new polymer system, a film preparation method, a new structure, a new filler and a new filling ratio, the preparation of the high-filling polymer solid electrolyte, the exertion of the advantages of easy film formation and good contact with electrodes of the polymer electrolyte and the further exertion of the advantages of inorganic electrolytes, and the preparation of the polymer solid electrolyte with high ionic conductance and high mechanical property is very necessary.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a preparation method of a polypropylene oxide based polymer solid electrolyte film with high room-temperature ionic conductivity, simple preparation process and good mechanical property. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) dissolving a polypropylene oxide precursor, an inorganic filler and a lithium salt in an organic solvent (such as N-methyl pyrrolidone), uniformly stirring and mixing, adding an initiator, and stirring for reaction to obtain a mixed slurry;
(2) and preparing a wet film (casting on a culture dish or blade coating on a glass plate) by using the mixed slurry, and then drying to obtain the solid electrolyte film.
In the above preparation method, preferably, the polypropylene oxide precursor is amino-terminated polypropylene oxide or methoxymethoxy-terminated polypropylene oxide. The polypropylene oxide precursor adopted by the invention is amino-terminated polypropylene oxide or silicon methoxy-terminated polypropylene oxide, is not pure polypropylene oxide, and is different from pure polypropylene oxide and polyethylene oxide-propylene oxide copolymer in chain segment structure and characteristics. The invention is favorable for interface combination and improvement of mechanical property in the battery assembling process based on high viscoelasticity and special framework structure, selects the polymer as the polymer, and further obtains high electrochemical property and mechanical property through modification of inorganic filler, organic additive (namely modifier) and the like. In addition, due to the adoption of the amino-terminated polypropylene oxide or the silicon methoxy-terminated polypropylene oxide, the dosage of the organic solvent adopted in the preparation process is allowed to be less, no special requirement is required for the preparation environment, the preparation process is more convenient and environment-friendly under the conventional atmosphere and without adopting a large amount of organic solvent. Also, the solid-state battery has a problem in that contact resistance of an electrode/electrolyte is large, and if the electrolyte has certain viscoelasticity, it is easier to combine, and contact resistance is smaller, and the present invention can achieve the above-mentioned effect of small contact resistance due to amino-terminated polypropylene oxide or methoxymethoxy-terminated polypropylene oxide.
In the above preparation method, preferably, the mass content of the inorganic filler is controlled to be 30-400% of the polypropylene oxide, and the mass content of the lithium salt is controlled to be 30-50% of the polypropylene oxide. The research shows that the uniformity of the formed film is influenced by adding too much inorganic filler and lithium salt, the electrochemical performance is influenced by adding too little inorganic filler and lithium salt, and the final film-forming performance, the mechanical performance and the electrochemical performance are excellent by controlling the mass content of the inorganic filler and the lithium salt. Particularly, the mass content of the inorganic filler in the invention is more preferably 300-400% of polypropylene oxide, and the invention adopts specific monomers, because of the optimization of a reaction system and a reaction process, the inclusion of the inorganic filler is very high (the conventional system can not add too much inorganic filler), and the dosage can reach as high as 400%, so that the electrolyte of the invention has the characteristics of both polymer electrolyte and inorganic electrolyte, and the inorganic electrolyte generally has good thermal stability, mechanical strength, ionic conductivity and electrochemical window, has small side reaction to metallic lithium, can effectively inhibit the growth of lithium dendrite, and can overcome the defects of pure polymer. Therefore, the electrolyte obtained by the reaction system can fully play the roles of a polymer electrolyte and an inorganic electrolyte, can improve the thermodynamic and electrochemical properties of the electrolyte, improve the stability to metal lithium, have good processability, excellent electrochemical properties and relatively low production cost, and has more excellent comprehensive properties of the polymer electrolyte.
In the above preparation method, preferably, the inorganic filler includes at least one of zirconia, yttrium-stabilized zirconia, titania, lanthanum oxide, lanthanum zirconate, lithium lanthanum zirconium oxide and lithium lanthanum titanium oxide nanopowder, and the particle size of the inorganic filler is 10 nm to 0.5 μm.
In the above production method, preferably, the lithium salt includes at least one of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, and lithium tetrafluoroborate.
In the above preparation method, preferably, the initiator includes at least one of lithium difluorooxalato borate, lithium hexafluorophosphate and lithium tetrafluoroborate, and the amount of the initiator added is 1 to 5% of the polypropylene oxide precursor.
In the preparation method, preferably, the initiator is added, the modifier is added after the stirring reaction, the stirring reaction is carried out for 0.5 to 1 hour, the modifier comprises one or more of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, succinonitrile or ionic liquid, and the addition amount of the modifier is controlled to be 10 to 30 percent of the mass of the polypropylene oxide. The ionic liquid is an electrolyte which can conduct ions by itself, such as 1-ethyl-3-methylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolium hexafluorophosphate and the like, and is mainly used for improving the electrochemical performance of polypropylene oxide. The PEG, succinonitrile or ionic liquid with specific molecular weight is mainly used for improving the dissolution of lithium salt, the ionic conductivity of a system and the like and improving the ionic conductivity of the electrolyte. The dosage and adding time of the modifier need to be accurately controlled to ensure that the function of the modifier is fully exerted.
In the above preparation method, preferably, a doctor blade method is adopted when the wet film is prepared by using the mixed slurry, one of a cellulose film, a polypropylene fiber film and a polyethylene fiber film is used as a framework, the mixed slurry is doctor-coated on two sides of the framework, and the thickness of the wet film is controlled to be 100-300 microns.
In the preparation method, preferably, the initiator is added and then stirred to react for 3 to 6 hours; the drying is to dry the wet film by blowing at 80-100 ℃ for 4-6h, and then put the film into a vacuum drying oven at 80-100 ℃ for further drying for 12-15 h.
In the above production method, preferably, the solid electrolyte film has an ionic conductivity of 10-4-10-3S/cm, potential window of 4.5-5V, and tensile strength of 10-30 MPa.
In the above production method, the solid electrolyte thin film is preferably suitable for any one of lithium iron phosphate, lithium cobaltate, and a ternary battery.
The invention adopts the modified amino-terminated polypropylene oxide or the silicon methoxyl-terminated polypropylene oxide instead of pure polypropylene oxide to form a specific supporting framework to improve the mechanical property. Based on the specific polymerized monomer, the improvement of ionic conductivity is promoted by controlling the type, the particle size distribution and the content (high inorganic filler) of the filler and adding the modifier, so that the uniformity, the mechanical property and the electrochemical property of the formed film are excellent.
According to the invention, the inorganic filler, the polypropylene oxide, the lithium salt and the initiator are uniformly mixed, the polypropylene oxide-based solid electrolyte film is prepared by a scratch coating film-forming method, the flexibility and the electrochemical performance of the electrolyte are improved by modification methods such as increasing the content of the inorganic filler, adding a modifier and a fiber framework, and the like, and the formed solid electrolyte film has high room-temperature ionic conductivity, simple preparation process and easy large-scale production.
Compared with the prior art, the invention has the advantages that:
1. compared with the existing polypropylene oxide solid electrolyte, the polypropylene oxide polymer solid electrolyte film provided by the invention has higher electrochemical performance (such as room temperature ionic conductivity) and mechanical performance (such as tensile strength).
2. Compared with the existing polypropylene oxide solid electrolyte, the preparation method of the polypropylene oxide polymer solid electrolyte film provided by the invention is simple and controllable, has low cost and small pollution, and is easy for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an image showing the distribution of Zr element in zirconia in the polypropylene oxide-based polymer solid electrolyte film in example 1.
FIG. 2 is a stress-strain curve of the polypropylene oxide-based polymer solid electrolyte film of example 2.
FIG. 3 is a macroscopic and microscopic photograph of the polypropylene oxide-based polymer solid electrolyte thin film of example 4.
FIG. 4 is a stress-strain curve of the polypropylene oxide-based polymer solid electrolyte film of example 4.
Fig. 5 is an electrochemical impedance plot of the ionic conductivity of the plugged cell of example 4.
Fig. 6 is an electrochemical stability window of the polypropylene oxide-based polymer solid electrolyte membrane of example 4.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The following examples and comparative examples were all tested for various properties using conventional testing methods in the art, i.e., a universal testing machine was used to test the tensile strength of the electrolyte membrane; calculating the ionic conductivity of the electrolyte by measuring the impedance curve of the stainless steel plate (SS)/electrolyte (SE)/stainless steel plate (SS) clogging cell; measuring the oxidation-reduction potential of the SS/SE/Li battery between 0 and 6V by adopting a linear sweep voltammetry method, and determining the stable electrochemical window of the electrolyte; the electrochemical performance of the cell based on the composite solid electrolyte is tested by a button cell, namely, the button cell is assembled by using high-voltage ternary NCM622 or lithium cobaltate or lithium iron phosphate as a positive electrode material and adopting a traditional electrode preparation method and the prepared positive electrode, a lithium sheet negative electrode and an electrolyte membrane. And (3) analyzing and detecting the specific capacity and the cycle performance of the battery by utilizing constant-current charging and discharging.
Example 1:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) respectively weighing 0.6g of zirconia with the average particle size of 25nm, 2g of a silicon methoxy end-capped polypropylene oxide precursor and 0.8g of lithium salt bis (trifluoromethyl) sulfonyl imide, dissolving in 3g N-methyl pyrrolidone, and mechanically stirring and mixing at normal temperature;
(2) adding 0.1g of lithium difluoro (oxalato) borate as a certain amount of initiator into the solution, and continuously stirring for 3 hours;
(3) casting the mixed slurry in a culture dish to form a wet film;
(4) and (3) after the wet film is dried by air blowing at the temperature of 80 ℃ for 4 hours, putting the wet film into a vacuum drying oven at the temperature of 100 ℃ for continuous drying for 12 hours to obtain a finished film.
The finished product obtained in the embodiment has uniform membrane structure, uniform zirconium oxide distribution (as shown in figure 1), tensile strength of 12MPa and ionic conductivity of 3.2 multiplied by 10-4S/cm, the potential window reaches 4.5V. The initial specific capacity of the solid-state battery formed by the solid-state battery, the lithium iron phosphate anode and the metal lithium cathode reaches 156mAh/g, and the initial specific capacity is kept at 85% after 100 cycles under 0.5 ℃.
Example 2:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) respectively weighing 1.6g of lithium lanthanum zirconium oxide with the average particle size of 220nm, 2g of amino-terminated polypropylene oxide precursor and 1.0g of lithium salt lithium trifluoromethanesulfonate, dissolving in 5g N-methylpyrrolidone, and mechanically stirring and mixing at normal temperature;
(2) adding a certain amount of initiator lithium tetrafluoroborate 0.02g into the solution, and continuously stirring for 6 hours;
(3) casting the mixed slurry in a culture dish to form a wet film;
(4) and (3) after the wet film is dried by air blowing at the temperature of 80 ℃ for 6 hours, putting the wet film into a vacuum drying oven at the temperature of 100 ℃ for continuous drying for 12 hours to obtain a finished film.
The finished product obtained in the embodiment has a uniform membrane structure, the tensile strength reaches 18MPa (as shown in figure 2), and the ionic conductivity reaches 4.3 multiplied by 10-4S/cm, the potential window reaches 4.65V. The initial specific capacity of the solid-state battery formed by the solid-state battery, the lithium cobaltate anode and the metal lithium cathode reaches 166mAh/g, and the initial specific capacity is kept at 89% after 100 cycles under 0.5 ℃.
Example 3:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) adding an initiator in the step (2) of the embodiment 1 for reaction, then adding 0.6g of polyethylene glycol 400 modifier, and continuing stirring for reaction for 1 hour;
(2) casting the slurry into a culture dish to form a film, wherein the thickness of the wet film is 300 mu m;
(3) and (3) after the wet film is dried by air blowing at the temperature of 80 ℃ for 4 hours, putting the wet film into a vacuum drying oven at the temperature of 100 ℃ for continuous drying for 12 hours to obtain a finished film.
The finished product obtained in the embodiment has uniform membrane structure and smooth surface, the tensile strength reaches 11MPa, and the ionic conductivity reaches 5.26 multiplied by 10-4S/cm, the potential window reaches 4.7V. The initial specific capacity of the solid-state battery consisting of the lithium iron phosphate anode and the metallic lithium cathode reaches 168mAh/g, and the initial specific capacity is kept at 85% after 100 cycles under 0.5 ℃.
Example 4:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) adding an initiator in the step (2) of the embodiment 1 for reaction, then adding 0.6g of polyethylene glycol 400 modifier, and continuing stirring for reaction for 1 hour;
(2) spreading a polypropylene fiber framework on a glass substrate, and blade-coating the slurry into a film by using a blade coater, wherein the wet film thickness is 300 mu m;
(3) standing for 30 minutes after coating, drying the film by blowing at 80 ℃, drying for 4 hours, then placing the film into a vacuum drying oven at 100 ℃ for secondary drying, and drying for 12 hours to obtain the finished film.
The finished product obtained in the example has a uniform film structure, a smooth surface (as shown in fig. 3), a tensile strength of 30MPa (as shown in fig. 4), and an ionic conductivity of 5.24 × 10-4S/cm (as shown in FIG. 5), the potential window reached 4.7V (as shown in FIG. 6). The initial specific capacity of the solid-state battery formed by the lithium iron phosphate anode and the metallic lithium cathode reaches 168mAh/g, and 88% is maintained after 100 cycles under 0.5 ℃.
Example 5:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) after the initiator is added in the step (2) of the embodiment 2 for reaction, 0.2g of ionic liquid modifier is added, and the stirring is continued for 0.5 hour;
(2) spreading a polyethylene fiber film on a polytetrafluoroethylene plate, and blade-coating the slurry into a film by using a blade coater, wherein the thickness of a wet film is 100 mu m;
(3) standing for 30 minutes after coating, drying the film by blowing at 80 ℃, drying for 4 hours, then placing the film into a vacuum drying oven at 100 ℃ for secondary drying, and drying for 12 hours to finish film formation.
The finished product film obtained in the embodiment has the advantages of uniform structure, smooth surface, 24MPa of tensile strength and 4.56 multiplied by 10 of ionic conductivity-4S/cm, the potential window reaches 4.7V, the initial specific capacity of the solid-state battery formed by the solid-state battery, the lithium cobaltate anode and the metal lithium cathode reaches 172mAh/g, and the initial specific capacity is kept at 90% after 100 cycles under 0.5 ℃.
Example 6:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) respectively weighing 8g of lithium lanthanum titanium oxide with the average particle size of 20nm, 2g of silicon methoxy end-capped polypropylene oxide precursor and 1.0g of lithium salt lithium trifluoromethanesulfonate, dissolving in 8g N-methylpyrrolidone, and mechanically stirring and mixing at normal temperature
(2) Adding a certain amount of initiator lithium tetrafluoroborate 0.02g into the solution, and continuously stirring for 6 hours;
(3) then adding 0.6g of polyethylene glycol 400 modifier, and continuing stirring for 0.5 hour;
(4) spreading a polyethylene fiber film on a polytetrafluoroethylene plate, and blade-coating the slurry into a film by using a blade coater, wherein the thickness of a wet film is 100 mu m;
(5) standing for 30 minutes after coating, drying the film by blowing at 80 ℃, drying for 4 hours, then placing the film into a vacuum drying oven at 100 ℃ for secondary drying, and drying for 12 hours to finish film formation.
The finished product film obtained in the embodiment has the advantages of uniform structure, smooth surface, tensile strength of 27MPa and ionic conductivity of 7.42 multiplied by 10-4S/cm, the potential window reaches 5.0V, the initial specific capacity of the solid-state battery consisting of the lithium cobaltate anode and the metal lithium cathode reaches 175mAh/g, and the initial specific capacity is kept 88% after 200 cycles under 0.5 ℃.
Comparative example 1:
a preparation method of a polypropylene oxide polymer solid electrolyte film comprises the following steps:
(1) respectively weighing 0.2g of zirconia with the average particle size of 25nm, 2g of a silicon methoxy end-capped polypropylene oxide precursor and 0.8g of lithium salt bis (trifluoromethyl) sulfonyl imide, dissolving in 3g N-methyl pyrrolidone, and mechanically stirring and mixing at normal temperature;
(2) adding 0.1g of lithium difluoro (oxalato) borate as a certain amount of initiator into the solution, and continuously stirring for 3 hours;
(3) casting the mixed slurry in a culture dish to form a wet film;
(4) and (3) after the wet film is dried by air blowing at the temperature of 80 ℃ for 4 hours, putting the wet film into a vacuum drying oven at the temperature of 100 ℃ for continuous drying for 12 hours to obtain a finished film.
The finished product obtained in the comparative example has a uniform membrane structure, the tensile strength reaches 5MPa, and the ionic conductivity reaches1.62×10-4S/cm, the potential window reaches 4.35V. The initial specific capacity of the solid-state battery formed by the solid-state battery, the lithium iron phosphate anode and the metal lithium cathode reaches 142mAh/g, and the initial specific capacity is kept 65% after 100 cycles under 0.5 ℃.
Claims (10)
1. A preparation method of a polypropylene oxide polymer solid electrolyte film is characterized by comprising the following steps:
(1) dissolving a polypropylene oxide precursor, an inorganic filler and a lithium salt in an organic solvent, uniformly stirring and mixing, adding an initiator, and stirring for reaction to obtain a mixed slurry;
(2) and preparing a wet film by using the mixed slurry, and drying to obtain the solid electrolyte film.
2. The method of claim 1, wherein the polypropylene oxide precursor is an amino-terminated polypropylene oxide or a methoxymethoxy-terminated polypropylene oxide.
3. The method according to claim 1, wherein the inorganic filler is controlled to be 30 to 400% by mass of the polypropylene oxide, and the lithium salt is controlled to be 30 to 50% by mass of the polypropylene oxide.
4. The method according to claim 1, wherein the inorganic filler comprises at least one of zirconia, yttrium-stabilized zirconia, titania, lanthana, lanthanum zirconate, lithium lanthanum zirconium oxide, and lithium lanthanum titanium oxide nanopowder, and has a particle size of 10 nm to 0.5 μm.
5. The method of claim 1, wherein the lithium salt comprises at least one of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium triflate, lithium hexafluoroarsenate, and lithium tetrafluoroborate.
6. The method of claim 1, wherein the initiator comprises at least one of lithium difluorooxalato borate, lithium hexafluorophosphate, and lithium tetrafluoroborate, and is added in an amount of 1 to 5% of the polypropylene oxide precursor.
7. The preparation method of any one of claims 1 to 6, wherein an initiator is added for stirring reaction, then a modifier is added for stirring reaction for 0.5 to 1 hour, the modifier comprises one or more of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, succinonitrile or ionic liquid, and the addition amount of the modifier is controlled to be 10 to 30 percent of the mass of the polypropylene oxide.
8. The production method according to any one of claims 1 to 6, wherein a doctor blade method is used when producing a wet film from the mixed slurry, and one of a cellulose film, a polypropylene fiber film and a polyethylene fiber film is used as a skeleton.
9. The preparation method according to any one of claims 1 to 6, wherein the reaction is carried out for 3 to 6 hours with stirring after the initiator is added; the drying is to dry the wet film by blowing at 80-100 ℃ for 4-6h, and then put the film into a vacuum drying oven at 80-100 ℃ for further drying for 12-15 h.
10. The production method according to any one of claims 1 to 6, wherein the ion conductivity of the solid electrolyte thin film is 10-4-10-3S/cm, potential window of 4.5-5V, and tensile strength of 10-30 MPa.
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| CN114914534A (en) * | 2022-05-26 | 2022-08-16 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Polymer electrolyte, preparation method and application in lithium ion battery |
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