CN110957534A - Solid electrolyte membrane, method for producing same, and solid battery - Google Patents
Solid electrolyte membrane, method for producing same, and solid battery Download PDFInfo
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Abstract
The invention discloses a solid electrolyte membrane, a preparation method thereof and a solid battery. Wherein the method of preparing a solid electrolyte membrane comprises: mixing the fast ion conductor, the polymerizable monomer, the crosslinkable monomer, the polymer and the solvent, and performing ball milling to obtain a mixed material; mixing the mixed material with lithium salt and carrying out ball milling to obtain electrolyte slurry; defoaming and ageing the electrolyte slurry to obtain casting slurry; casting the casting slurry onto a base film, and carrying out heat treatment to form the casting slurry; removing the base film to obtain the solid electrolyte membrane. The method combines tape casting and thermal polymerization technology to prepare the ultrathin high-strength solid electrolyte membrane.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte membrane, a preparation method thereof and a solid battery.
Background
Solid-state batteries are considered to be the direction of future lithium ion battery development due to their higher energy density and safety. The solid electrolyte is adopted to replace the liquid electrolyte, so that the thermal runaway of the battery can be inhibited, the battery can endure a high-temperature working environment, and meanwhile, the anode and cathode materials with higher gram capacity can be matched, so that the energy density of the battery is improved. The current solid electrolyte is mainly researched in an organic-inorganic composite electrolyte system, and is mainly obtained by a coating and casting method, and the thickness of the composite electrolyte membrane is usually more than 50 micrometers, even 100-200 micrometers. On one hand, the transmission path of lithium ions through the electrolyte membrane is long, the battery resistance is large, and the electrical property is poor; the electrolyte membrane has poor strength, increases difficulty for manufacturing and assembling the battery, and is difficult to be applied in industrialization. On the other hand, many of the preparation methods can only be realized in a laboratory, and are difficult to popularize industrially, and even if popularization possibility exists, related technical reserves are insufficient, and a production line and equipment need to be redesigned.
Thus, the existing solid-state batteries still need to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a solid electrolyte membrane, a method for producing the same, and a solid-state battery. Among them, the method for preparing the solid electrolyte membrane can prepare an ultra-thin, high-strength solid electrolyte membrane by combining tape casting with a thermal polymerization technique.
The present invention provides a method of preparing a solid electrolyte membrane, according to an embodiment of the present invention, the method comprising:
and (3) material mixing: mixing the fast ion conductor, the polymerizable monomer, the crosslinkable monomer, the polymer and the solvent, and performing ball milling to obtain a mixed material;
and (3) mixing lithium salt: mixing the mixed material with lithium salt and carrying out ball milling to obtain electrolyte slurry;
defoaming and ageing the slurry: defoaming and ageing the electrolyte slurry to obtain casting slurry;
slurry casting and heat treatment: casting the casting slurry onto a base film, and carrying out heat treatment to form the casting slurry;
removing the base film: removing the base film to obtain the solid electrolyte membrane.
According to the method for preparing the solid electrolyte membrane of the embodiment of the invention, the electrolyte slurry containing the polymerizable monomer and the crosslinkable monomer is prepared, and the casting slurry for casting is obtained after the electrolyte slurry is defoamed and aged. Subsequently, the casting slurry is applied to the base film by the casting technique, the thickness of the casting film can be precisely controlled, a thinner composite electrolyte membrane precursor is obtained, and pores in the interior and on the surface of the electrolyte membrane can be effectively reduced. Furthermore, through heat treatment, the solvent in the composite electrolyte membrane is removed, meanwhile, the polymerizable monomer and the crosslinkable monomer are subjected to thermal polymerization, and the ultrathin high-strength solid electrolyte membrane is obtained through molding, so that an initiator is not required to be additionally added to initiate the monomer polymerization, and the deterioration effect of the initiator on the battery performance is avoided. And after the solid electrolyte membrane is formed, separating and removing the base membrane to obtain a solid electrolyte membrane product.
In addition, the method of manufacturing a solid electrolyte membrane according to the above-described embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, in the step of mixing the materials, the fast ion conductor, the polymerizable monomer, the crosslinkable monomer, and the solvent are mixed to obtain a first mixture; mixing the polymer with the solvent to obtain a second mixed material; mixing the first mixed material and the second mixed material and performing ball milling to obtain a mixed material; or mixing the fast ion conductor, the polymerizable monomer and the crosslinkable monomer to obtain a third mixed material; and mixing the third mixture with the polymer and the solvent, and performing ball milling to obtain the mixed material.
In some embodiments of the present invention, the fast ion conductor comprises at least one selected from the group consisting of garnet-type lithium ion conductors, perovskite-type lithium ion conductors, LISICON-type lithium ion conductors, NASICON-type lithium ion conductors, sulfide solid state electrolytes.
In some embodiments of the present invention, the polymerizable monomer comprises at least one selected from castor oil, acrylonitrile, methyl methacrylate, carbonate, epoxidized ethylene, vinylidene fluoride.
In some embodiments of the invention, the crosslinkable monomer comprises at least one selected from the group consisting of butadiene, maleic anhydride, castor oil, soybean oil, succinonitrile, maleic anhydride, ethyl butadienate, divinylbenzene, diisocyanate, N-methylenebisacrylamide.
In some embodiments of the invention, the polymer comprises at least one selected from the group consisting of polyether, polyacrylonitrile, polymethyl methacrylate, polycarbonate, polyethylene oxide, polyimide.
In some embodiments of the invention, the solvent comprises at least one selected from the group consisting of N-methylpyrrolidone, acetonitrile, ethanol, xylene, N-dimethylformamide.
In some embodiments of the invention, the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato borate, lithium difluoro-oxalato borate, lithium tetrafluoroborate, lithium hexafluoroarsenate.
In some embodiments of the present invention, in the electrolyte slurry, the mass content of the fast ion conductor is 5 to 35%, the mass content of the polymerizable monomer is 0.5 to 10%, the mass content of the crosslinkable monomer is 0.1 to 20%, the mass content of the polymer is 40 to 85%, and the mass content of the lithium salt is 5 to 30%.
In some embodiments of the present invention, the fast ion conductor has an average particle size of 10 to 500 nm.
In some embodiments of the present invention, the temperature used for the heat treatment is 60 to 200 ℃.
In another aspect of the invention, the invention features a solid electrolyte membrane. According to the embodiment of the invention, the solid electrolyte membrane is produced by the method of producing a solid electrolyte membrane of the above embodiment. Therefore, the solid electrolyte membrane has the advantages of ultra-thinness, high strength and the like, and does not contain a polymer initiator, so that the performance of the battery is not adversely affected.
In addition, the solid electrolyte membrane according to the above-described embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, the solid electrolyte membrane has a thickness of 9 to 30 μm.
In yet another aspect of the present invention, a solid-state battery is provided. According to an embodiment of the present invention, the solid-state battery includes: a composite positive electrode, the solid electrolyte membrane of the above example, and a composite negative electrode. Thus, the solid-state battery has all the features and advantages described above for the solid electrolyte membrane, and thus, a detailed description thereof is omitted. In general, the solid-state battery has excellent rate performance, cycle performance and other electrical properties.
In still another aspect of the present invention, the present invention provides a method of manufacturing the solid-state battery of the above embodiment. According to an embodiment of the invention, the method comprises: a solid electrolyte membrane was prepared according to the method for preparing a solid electrolyte membrane of the above example; mixing a second polymer, lithium salt and a solvent to obtain an interfacial wetting agent; applying the interfacial wetting agent to a positive plate and a negative plate respectively so as to form wetting layers on the surfaces of the positive plate and the negative plate and obtain a composite positive electrode and a composite negative electrode respectively; and preparing the solid-state battery by using the solid electrolyte membrane, the composite positive electrode and the composite negative electrode. The method is simple and convenient to operate and easy to implement industrially, and the prepared solid-state battery has excellent rate performance, cycle performance and other electrical properties.
In addition, the method of manufacturing a solid-state battery according to the above-described embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the second polymer comprises at least one selected from the group consisting of polyacrylate, polycarbonate.
In some embodiments of the invention, the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato borate, lithium difluoro-oxalato borate, lithium tetrafluoroborate, lithium hexafluoroarsenate.
In some embodiments of the present invention, in the interfacial wetting agent, the mass fraction of the second polymer is 2 to 50%, and the mass fraction of the lithium salt is 20 to 60%.
In some embodiments of the invention, the wetting layer has a thickness of 50nm to 5 μm.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of making a solid electrolyte membrane according to one embodiment of the invention;
fig. 2 is a graph showing the results of rate performance tests of the solid-state battery prepared in example 1;
fig. 3 is a graph showing the results of cycle performance tests of the solid-state battery prepared in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the present invention, a method of making a solid electrolyte membrane is presented. According to an embodiment of the invention, the method comprises: mixing the fast ion conductor, the polymerizable monomer, the crosslinkable monomer, the polymer and the solvent, and performing ball milling to obtain a mixed material; mixing the mixed material with lithium salt and carrying out ball milling to obtain electrolyte slurry; defoaming and ageing the electrolyte slurry to obtain casting slurry; casting the casting slurry on a base film, and carrying out heat treatment to form the casting slurry; the base film was removed to obtain a solid electrolyte membrane.
The method of producing a solid electrolyte membrane according to an embodiment of the invention is described in further detail below. Referring to fig. 1, the method includes:
s100: obtaining a mixture
In the step, a fast ion conductor, a polymerizable monomer, a crosslinkable monomer, a polymer and a solvent are mixed and subjected to ball milling to obtain a mixed material; specifically, the fast ion conductor, the polymerizable monomer and the crosslinkable monomer can be mixed with a solvent and subjected to ball milling (the ball milling rotation speed can be 400-1500 rpm) to obtain a first mixed material; mixing a polymer and a solvent, carrying out ball milling (the ball milling rotation speed can be 100-1000 rpm) to obtain a second mixed material, and then mixing the first mixed material and the second mixed material, and carrying out ball milling to obtain the mixed material; or mixing the fast ion conductor, the polymerizable monomer and the crosslinkable monomer, mixing with the polymer and the solvent, and performing ball milling to obtain the mixed material. The invention adopts the polymerizable monomer and the crosslinkable monomer as the raw materials of the solid electrolyte membrane, and can polymerize the monomer through subsequent heat treatment without adding a polymerization initiator or a crosslinking initiator which influences the performance of the battery additionally.
According to some embodiments of the present invention, the fast ion conductor may include at least one selected from a garnet-type lithium ion conductor, a perovskite-type lithium ion conductor, a LISICON-type lithium ion conductor, a NASICON-type lithium ion conductor, and a sulfide solid electrolyte, and preferably is a garnet-type lithium ion conductor. Thereby, a better lithium ion conductivity can be provided.
According to some embodiments of the invention, the fast ion conductor is provided in the form of a powder. The average particle diameter of the fast ion conductor powder may be 10 to 500nm, for example, 10nm, 50nm, 100nm, 200nm, 250nm, 300nm, 400nm, 500nm, etc. By controlling the particle size of the fast ion conductor within the above range, the flatness and uniformity of the solid electrolyte membrane to be formed subsequently can be further improved.
According to some embodiments of the present invention, the polymerizable monomer may include at least one selected from the group consisting of castor oil, acrylonitrile, methyl methacrylate, carbonate, epoxidized ethylene, and vinylidene fluoride. The crosslinkable monomer may include at least one selected from the group consisting of butadiene, maleic anhydride, castor oil, soybean oil, succinonitrile, maleic anhydride, ethyl butadienate, divinylbenzene, diisocyanate, and N, N-methylenebisacrylamide. The polymerizable monomer and the crosslinkable monomer can form a polymer under the heating condition without the action of an initiator, and the formed polymer can remarkably improve the mechanical strength of the solid electrolyte membrane.
According to some embodiments of the present invention, the polymer may include at least one selected from the group consisting of polyether, polyacrylonitrile, polymethyl methacrylate, polycarbonate, polyethylene oxide, and polyimide. This can further improve the mechanical strength of the solid electrolyte membrane.
According to some embodiments of the present invention, the solvent may include at least one selected from the group consisting of N-methylpyrrolidone, acetonitrile, ethanol, xylene, and N, N-dimethylformamide. Such solvents can disperse polymerizable monomers, crosslinkable monomers, polymers, lithium salts, etc. well and are easily removed in subsequent steps.
S200: obtaining an electrolyte slurry
In the step, the above mixed material and lithium salt are mixed and ball-milled to obtain electrolyte slurry. Specifically, the second mixture can be added into the first mixture to obtain a mixed material, and a lithium salt is added, and the ball milling is continued for 8-15 h (preferably 12h) to obtain an electrolyte slurry.
According to some embodiments of the present invention, the lithium salt may include at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato borate, lithium difluoro-oxalato borate, lithium tetrafluoroborate, and lithium hexafluoroarsenate. Thereby, the electrical properties of the solid electrolyte membrane can be further improved.
According to some embodiments of the present invention, in the above electrolyte slurry, the mass content of the fast ion conductor may be 5 to 35% (e.g., 5%, 10%, 20%, 30%, 35%, etc.), the mass content of the polymerizable monomer may be 0.5 to 10% (e.g., 0.5%, 1%, 3%, 5%, 8%, 10%, etc.), the mass content of the crosslinkable monomer may be 0.1 to 20% (e.g., 0.1%, 0.5%, 1%, 5%, 8%, 10%, 12%, 15%, 20%, etc.), the mass content of the polymer may be 40 to 85% (e.g., 40%, 50%, 60%, 70%, 85%, etc.), and the mass content of the lithium salt may be 5 to 30% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, etc.).
S300: defoaming and ageing treatment
In the step, defoaming treatment and ageing treatment are carried out on the electrolyte slurry to obtain the tape-casting slurry. Specifically, the electrolyte slurry can be defoamed under negative pressure to a certain viscosity, for example 1600-6500 Pa · s, and then aged for 2-6 h. Thus, the electrical properties of the solid electrolyte membrane prepared subsequently can be further improved.
S400: tape casting and heat treatment molding
In this step, the casting slurry is cast onto the base film, and heat treatment is performed to shape the casting slurry. According to some embodiments of the present invention, after the casting slurry is cast onto the base film, the thickness of the casting film can be precisely controlled by adjusting the height of the casting blade and the casting bucket, and then the oven in the casting machine is used to dry the casting film, so that the polymerizable monomer and the crosslinkable monomer in the casting film form a polymer, and the thermal forming is completed.
According to some embodiments of the present invention, the temperature used for the heat treatment may be 60 to 200 ℃, such as 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 160 ℃, 180 ℃, 200 ℃ and the like. By performing the heat treatment at the above temperature, the polymerizable monomer and the crosslinkable monomer in the casting film can be further facilitated to form a polymer, and the mechanical strength of the obtained solid electrolyte membrane can be further improved.
According to some embodiments of the present invention, the base film may be a PET base film.
S500: removing the base film
In this step, the base film is removed to obtain a solid electrolyte membrane. According to some embodiments of the present invention, the solid electrolyte membrane may be separated from the base membrane at the end of the casting machine to obtain a solid electrolyte membrane product.
In another aspect of the invention, the invention features a solid electrolyte membrane. According to the embodiment of the invention, the solid electrolyte membrane is produced by the method of producing a solid electrolyte membrane of the above embodiment. Therefore, the solid electrolyte membrane has the advantages of ultra-thinness, high strength and the like, and does not contain a polymer initiator, so that the performance of the battery is not adversely affected.
According to some embodiments of the present invention, the thickness of the solid electrolyte membrane may be 9 to 30 μm, such as 9 μm, 10 μm, 16 μm, 20 μm, 25 μm, 30 μm, etc., with thickness variation ranging ± 1 μm. The solid electrolyte membrane is prepared by the combined process of tape casting and thermal polymerization, has small thickness and can be accurately regulated and controlled; meanwhile, the solid electrolyte membrane has small thickness and large capacity, and the energy density is correspondingly improved. If the thickness of the solid electrolyte membrane is too large, the lithium ion transmission path is too long and the internal resistance is increased.
In yet another aspect of the present invention, a solid-state battery is provided. According to an embodiment of the present invention, the solid-state battery includes: a composite positive electrode, the solid electrolyte membrane of the above example, and a composite negative electrode. Thus, the solid-state battery has all the features and advantages described above for the solid electrolyte membrane, and thus, a detailed description thereof is omitted. In general, the solid-state battery has excellent rate performance, cycle performance and other electrical properties.
According to some embodiments of the present invention, the composite positive electrode has a positive active material commonly used in the art, such as at least one of lithium iron phosphate, lithium iron manganese phosphate, lithium manganate, lithium cobaltate, nickel cobalt manganese ternary positive electrode material, and nickel cobalt aluminum ternary positive electrode material. The composite anode has thereon or is formed of an anode active material commonly used in the art, such as metallic lithium or a lithium alloy.
In addition, it should be noted that the solid-state battery further includes a case, and conventional components of the positive and negative external terminals, which are not described in detail herein.
In still another aspect of the present invention, the present invention provides a method of manufacturing the solid-state battery of the above embodiment. According to an embodiment of the invention, the method comprises: a solid electrolyte membrane was prepared according to the method for preparing a solid electrolyte membrane of the above example; mixing a second polymer, lithium salt and a solvent to obtain an interfacial wetting agent; respectively applying an interfacial wetting agent to the positive plate and the negative plate so as to form wetting layers on the surfaces of the positive plate and the negative plate and respectively obtain a composite positive electrode and a composite negative electrode; and preparing the solid-state battery by using the solid-state electrolyte membrane, the composite positive electrode and the composite negative electrode. The method is simple and convenient to operate and easy to implement industrially, and the prepared solid-state battery has excellent rate performance, cycle performance and other electrical properties.
According to some embodiments of the invention, the second polymer comprises at least one selected from the group consisting of polyacrylate and polycarbonate. This can further improve the high voltage resistance of the solid-state battery.
According to some embodiments of the invention, the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato borate, lithium difluoro-oxalato borate, lithium tetrafluoroborate and lithium hexafluoroarsenate. Thereby, the electrical performance of the solid-state battery can be further improved.
According to some embodiments of the present invention, in the interfacial wetting agent, the mass fraction of the second polymer may be 2 to 50% (e.g., 2%, 10%, 20%, 30%, 40%, 50%, etc.), and the mass fraction of the lithium salt may be 20 to 60% (e.g., 20%, 30%, 40%, 50%, 60%, etc.). Therefore, the wetting effect between the anode and the cathode and the solid electrolyte membrane can be further improved, and the electrical property of the solid-state battery can be improved.
According to some embodiments of the present invention, the thickness of the wetting layer may be 50nm to 5 μm, such as 50nm, 100nm, 500nm, 1 μm, 2 μm, 3 μm, 5 μm, and the like. Therefore, the wetting effect between the anode and the cathode and the solid electrolyte membrane can be further improved, and the electrical property of the solid-state battery can be improved.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Dispersing lithium lanthanum zirconium oxygen garnet type lithium ion conductors with the average particle size of 200nm and the mass ratio of 30 percent, methyl acrylate with the mass ratio of 5 percent and divinylbenzene with the mass ratio of 10 percent into an N-methyl pyrrolidone solvent, and performing ball milling at the rotating speed of 800rpm to obtain a solution A; dispersing 45 mass percent of polycarbonate into an N-methyl pyrrolidone solvent, and carrying out ball milling at the rotating speed of 300rpm to obtain a solution B; adding the solution B into the solution A, adding 25 mass percent of lithium hexafluorophosphate, and continuing ball milling for 12 hours to obtain electrolyte slurry;
(2) defoaming the electrolyte slurry under negative pressure to a certain viscosity, and then aging for 4 hours;
(3) and (3) casting the slurry obtained in the step (2) onto a PET (polyethylene terephthalate) base film by adopting a casting forming technology, regulating the thickness of the electrolyte film by adjusting the height of a casting knife and a casting hopper, drying the electrolyte film by an oven in the middle of a casting machine, baking the electrolyte film for 30min at 150 ℃, and separating the electrolyte film from the PET base film at the tail of the casting machine to obtain a composite solid electrolyte film with the thickness of 10 mu m, wherein the fluctuation range of the thickness is +/-1 mu m.
(4) Dispersing 15% by mass of polycarbonate polymer and 20% by mass of lithium hexafluorophosphate into an electrolyte solvent, heating and stirring for 2 hours, standing and cooling to room temperature to obtain an interface wetting agent;
(5) the interface wetting agent is printed on LiNi by adopting a screen printing technology0.5Co0.2Mn0.3Obtaining a composite positive pole piece and a composite negative pole piece with the wetting layer thickness of 1 mu m on the surfaces of the pole pieces on the positive pole piece and the lithium metal negative pole piece;
(6) and assembling and hot-pressing the battery by adopting a lamination process according to the structure of the composite anode/the composite solid electrolyte membrane/the composite lithium cathode to obtain the battery core of the solid battery.
The product was tested for rate capability and cycle performance, and the results are shown in fig. 2 and 3.
Example 2
(1) Dispersing lithium lanthanum zirconium oxygen garnet type lithium ion conductors with the average grain diameter of 50nm and the mass ratio of 25 percent, butadiene with the mass ratio of 10 percent and acrylic ester with the mass ratio of 5 percent into an N-methyl pyrrolidone solvent, and performing ball milling at the rotating speed of 600rpm to obtain a solution A; dispersing 55 mass percent of polycarbonate into an N-methyl pyrrolidone solvent, and performing ball milling at the rotating speed of 200rpm to obtain a solution B; adding the solution B into the solution A, adding 20 mass percent of bis (trifluoromethyl) sulfonyl imide lithium, and continuing ball milling for 12 hours to obtain electrolyte slurry;
(2) defoaming the electrolyte slurry under negative pressure to a certain viscosity, and then aging for 4 hours;
(3) and (3) casting the slurry obtained in the step (2) onto a PET (polyethylene terephthalate) base film by adopting a casting forming technology, regulating the thickness of the electrolyte film by adjusting the height of a casting knife and a casting hopper, drying the electrolyte film by an oven in the middle of a casting machine, baking the electrolyte film for 10min at 160 ℃, and separating the electrolyte film from the PET base film at the tail of the casting machine to obtain a composite solid electrolyte film with the thickness of 16 mu m, wherein the fluctuation range of the thickness is +/-1 mu m.
(4) Dispersing 8% by mass of polycarbonate polymer and 35% by mass of lithium hexafluorophosphate into an electrolyte solvent, heating and stirring for 2 hours, standing and cooling to room temperature to obtain an interface wetting agent;
(5) printing the interface wetting agent on a lithium iron phosphate positive plate and a lithium tin alloy negative plate by adopting a screen printing technology to obtain a composite positive plate and a composite negative plate with the wetting layer on the surface of the plates being 500nm in thickness;
(6) and assembling and hot-pressing the battery by adopting a winding process according to the structure of the composite anode/the composite solid electrolyte membrane/the composite lithium cathode to obtain the battery core of the solid battery.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., 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 are not necessarily intended to 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. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making a solid electrolyte membrane, comprising:
and (3) material mixing: mixing the fast ion conductor, the polymerizable monomer, the crosslinkable monomer, the polymer and the solvent, and performing ball milling to obtain a mixed material;
and (3) mixing lithium salt: mixing the mixed material with lithium salt and carrying out ball milling to obtain electrolyte slurry;
defoaming and ageing the slurry: defoaming and ageing the electrolyte slurry to obtain casting slurry;
slurry casting and heat treatment: casting the casting slurry onto a base film, and carrying out heat treatment to form the casting slurry;
removing the base film: removing the base film to obtain the solid electrolyte membrane.
2. The method for producing a solid electrolyte membrane according to claim 1, wherein, in the step of mixing materials,
mixing the fast ion conductor, the polymerizable monomer, the crosslinkable monomer and the solvent to obtain a first mixed material; mixing the polymer with the solvent to obtain a second mixed material; mixing the first mixed material and the second mixed material and performing ball milling to obtain a mixed material;
or mixing the fast ion conductor, the polymerizable monomer and the crosslinkable monomer to obtain a third mixed material; and mixing the third mixture with the polymer and the solvent, and performing ball milling to obtain the mixed material.
3. The method of producing a solid electrolyte membrane according to claim 1, wherein the fast ion conductor comprises at least one selected from a garnet-type lithium ion conductor, a perovskite-type lithium ion conductor, a LISICON-type lithium ion conductor, a NASICON-type lithium ion conductor, a sulfide solid electrolyte;
optionally, the polymerizable monomer comprises at least one selected from castor oil, acrylonitrile, methyl methacrylate, carbonate, epoxidized ethylene, vinylidene fluoride;
optionally, the crosslinkable monomer comprises at least one selected from butadiene, maleic anhydride, castor oil, soybean oil, succinonitrile, maleic anhydride, ethyl butadienate, divinylbenzene, diisocyanate, N-methylenebisacrylamide;
optionally, the polymer comprises at least one selected from the group consisting of polyether, polyacrylonitrile, polymethylmethacrylate, polycarbonate, polyethylene oxide, polyimide;
optionally, the solvent comprises at least one selected from the group consisting of N-methylpyrrolidone, acetonitrile, ethanol, xylene, N-dimethylformamide;
optionally, the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato-borate, lithium difluoro-oxalato-borate, lithium tetrafluoroborate, lithium hexafluoroarsenate.
4. The method for producing a solid electrolyte membrane according to claim 1, wherein the mass content of the fast ion conductor in the electrolyte slurry is 5 to 35%, the mass content of the polymerizable monomer is 0.5 to 10%, the mass content of the crosslinkable monomer is 0.1 to 20%, the mass content of the polymer is 40 to 85%, and the mass content of the lithium salt is 5 to 30%.
5. The method for producing a solid electrolyte membrane according to claim 1, wherein the fast ion conductor has an average particle diameter of 10 to 500 nm;
optionally, the temperature adopted by the heat treatment is 60-200 ℃.
6. A solid electrolyte membrane produced by the method for producing a solid electrolyte membrane according to any one of claims 1 to 5;
optionally, the thickness of the solid electrolyte membrane is 9-30 μm.
7. A solid-state battery, comprising:
compounding a positive electrode;
the solid electrolyte membrane of claim 6;
and (4) compounding the negative electrode.
8. A method of producing the solid-state battery of claim 7, comprising:
preparing a solid electrolyte membrane according to the method of any one of claims 1 to 5;
mixing a second polymer, lithium salt and a solvent to obtain an interfacial wetting agent;
applying the interfacial wetting agent to a positive plate and a negative plate respectively so as to form wetting layers on the surfaces of the positive plate and the negative plate and obtain a composite positive electrode and a composite negative electrode respectively;
and preparing the solid-state battery by using the solid electrolyte membrane, the composite positive electrode and the composite negative electrode.
9. The method of claim 8, wherein the second polymer comprises at least one selected from the group consisting of a polyacrylate, a polycarbonate;
optionally, the lithium salt comprises at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bis-oxalato-borate, lithium difluoro-oxalato-borate, lithium tetrafluoroborate, lithium hexafluoroarsenate;
optionally, in the interfacial wetting agent, the mass fraction of the second polymer is 2-50%, and the mass fraction of the lithium salt is 20-60%.
10. The method of claim 8, wherein the wetting layer has a thickness of 50nm to 5 μm.
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