CN112635820A - Lithiation modified rod-like ceramic filler and its preparation method and application - Google Patents
Lithiation modified rod-like ceramic filler and its preparation method and application Download PDFInfo
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a lithiation modified rod-shaped ceramic filler, which comprises: a rod-like ceramic filler and lithium-containing oxide particles; wherein the rod-shaped ceramic filler is selected from Al2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2One or more than two of nanowires or nanofibers; the lithium-containing oxide particles include: one or more than two of Li-Al-O, Li-Ti-O, Li-Zr-O. The invention improves the Lewis acid sites on the surface of the rod-shaped ceramic filler by carrying out lithiation treatment on the surface of the rod-shaped ceramic filler, combines the advantages of inert filler and fast ion conductor, and achieves the performance of the fast ion conductorAnd the environmental adaptability is improved, and the material cost is reduced. In addition, the lithiation modified rod-shaped ceramic filler provided by the invention can be applied to the preparation of a composite solid electrolyte, and can greatly improve the ionic conductivity of the composite solid electrolyte.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a lithiation modified rod-shaped ceramic filler as well as a preparation method and application thereof.
Background
The preparation of the composite solid electrolyte by adopting the organic/inorganic composite is the preparation technology with the most application prospect at present. The incorporation of nano-or micro-particles as fillers into the host polymer during the preparation of the composite solid electrolyte may improve the ionic conductivity and mechanical stability of the electrolyte. Studies have shown that the migration of lithium ions in the electrolyte is coupled with the segmental motion of the polymer chains. The addition of the nanoparticles prevents local recombination of chains in the polymer, and can reduce crystallization of the polymer, thereby facilitating the migration of high lithium ions. Meanwhile, the theoretical basis of the increase of the ionic conductivity is also strongly supported by the interaction mechanism of the Lewis acid-base model. However, most inorganic fillers are added to polymers in the form of nano-or submicron particles and are randomly distributed, failing to form continuous example transmission paths, which limits the ionic conductivity of the polymer electrolyte. Currently, one-dimensional or quasi-one-dimensional materials are receiving much attention because they can provide a relatively continuous ion transport path, such as researchers add LLZO nanowires, LLTO nanowires, etc. to polyethylene oxide to promote the dissociation of lithium salts, thereby resulting in high ionic conductivity. However, these fast ion conductor fillers generally have high cost and poor environmental suitability, and are liable to react with air, moisture or lithium metal, and thus are difficult to be widely popularized in practical applications.
In recent years, researchers have found that some inert fillers, such as yttrium oxide (Y)2O3) Doped zirconia (ZrO)2) Nanowire and Polyacrylonitrile (PAN) composite TiO2The nano-rod is compounded with the polycarbonate, so that the ionic conductivity of the polymer can be improved to a certain extent, and the nano-rod has high stability, low cost and convenient preparation. However, compared to fast ionsThe conductor, these rod-like ceramic inert fillers have limited effect of enhancing the ionic conductivity of the polymer, mainly because the inert fillers react weakly with lithium salts, the lewis acid base of the polymer, resulting in a lower number of free lithium ions.
Therefore, there is a need for a modified filler for solid electrolyte applications to combine the advantages of inert filler and fast ion conductor to achieve the technical effect of improving the ionic conductivity of solid electrolyte.
Disclosure of Invention
In view of the above problems, the present invention provides a lithiation modified rod-like ceramic filler, and a preparation method and applications thereof. According to the invention, the surface of the rod-shaped ceramic filler is subjected to lithiation treatment, so that Lewis acid sites on the surface of the rod-shaped ceramic filler are increased, the obtained lithiation modified rod-shaped ceramic filler combines the advantages of an inert filler and a fast ion conductor, the level of the fast ion conductor is achieved in performance, the environmental adaptability is improved, and the material cost is reduced. In addition, the lithiation modified rod-shaped ceramic filler provided by the invention can be applied to the preparation of a composite solid electrolyte, and can greatly improve the ionic conductivity of the composite solid electrolyte.
The technical scheme of the invention for realizing the purpose is as follows:
in one aspect of the present invention, there is provided a lithiated modified rod-shaped ceramic filler, wherein the lithiated modified rod-shaped ceramic filler comprises: a rod-like ceramic filler and lithium-containing oxide particles;
wherein the rod-shaped ceramic filler is selected from Al2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2One or more than two of nanowires or nanofibers;
the lithium-containing oxide particles include: one or more than two of Li-Al-O, Li-Ti-O, Li-Zr-O.
In some embodiments of the invention, the lithiated modified rod-like ceramic filler of the invention, the lithium-containing oxide particles comprise: LiAlO2、LiAl5O8、LiTiO2、Li2Ti2O4、Li4Ti5O12、Li2ZrO3、Li4ZrO4One or more than two of them.
In some embodiments of the invention, the lithiated modified rod-shaped ceramic filler of the invention comprises lithium-containing oxide particles coated on the surface of the rod-shaped ceramic filler.
In some embodiments of the invention, the lithiated modified rod-like ceramic filler has a diameter of 20 to 200 nm and a length of 1 to 50 μm.
In some embodiments of the present invention, the lithiated modified rod-like ceramic filler of the present invention has lithium-containing oxide particles having a particle size of 20 nm or less.
In some preferred embodiments of the present invention, in the lithiated modified rod-shaped ceramic filler, the diameter of the lithiated modified rod-shaped ceramic filler is 100 to 200 nanometers, and the length of the lithiated modified rod-shaped ceramic filler is 20 to 45 micrometers.
In some embodiments of the present invention, in the lithiated modified rod-like ceramic filler of the present invention, the mass ratio of the lithium-containing oxide particles to the lithiated modified rod-like ceramic filler is (1 to 15): 100.
in some preferred embodiments of the present invention, in the lithiated modified rod-like ceramic filler of the present invention, the mass ratio of the lithium-containing oxide particles to the lithiated modified rod-like ceramic filler is (8 to 14): 100.
in some preferred embodiments of the present invention, in the lithiated modified rod-shaped ceramic filler according to the present invention, the mass ratio of the lithium-containing oxide particles to the lithiated modified rod-shaped ceramic filler is 14.7: 100.
in another aspect of the present invention, there is also provided a method for preparing the lithiated modified rod-like ceramic filler according to the present invention, including:
mixing the rod-shaped ceramic filler with ionic water containing lithium salt, and stirring to obtain a suspension;
adjusting the pH value of the suspension to 8-10, and then reacting at the temperature of 140-200 ℃ for 2-10 h to obtain a reaction solution;
adjusting the pH value of the reaction solution to 7-8, and then filtering to obtain a precipitate;
washing the precipitate to obtain a washed precipitate;
drying the washed precipitate at the temperature of 80-100 ℃ for 12-24 h, and then sintering at the temperature of 400-800 ℃ for 2-6 h to obtain the lithiation modified rodlike ceramic filler;
wherein the lithium salt is selected from one or more of lithium acetate, lithium nitrate and lithium chloride.
In some embodiments of the present invention, the lithiated modified rod-shaped ceramic filler is selected from Al in the methods of the present invention2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2One or more than two of the nano-wires or nano-fibers.
In some embodiments of the present invention, the method of preparing a lithiated modified rod-shaped ceramic filler according to the present invention, the lithiated modified rod-shaped ceramic filler comprises: lithium-containing oxide particles and the rod-like ceramic filler.
In some embodiments of the invention, in the methods of preparing lithiated modified rod-shaped ceramic fillers described herein, the lithium-containing oxide particles comprise: one or more than two of Li-Al-O, Li-Ti-O, Li-Zr-O;
in some embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, the ratio of the mass of the rod-shaped ceramic filler to the volume of the ionic water containing a lithium salt is (2-3) g: 15 mL.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, the ratio of the mass of the rod-shaped ceramic filler to the volume of the ionic water containing a lithium salt is 1 g: 6 mL.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-like ceramic filler according to the present invention, in the ionic water containing the lithium salt, the mass ratio of the lithium salt to the ionic water containing the lithium salt is (2-3): 25.
in some preferred embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, the mass ratio of the lithium salt to the ionic water containing the lithium salt is 1: 10.
in some preferred embodiments of the present invention, the method for preparing the lithiated modified rod-shaped ceramic filler according to the present invention comprises:
adding the Al2O3Mixing the nanowires with ionic water containing lithium acetate, and stirring to obtain a suspension;
adjusting the pH value of the suspension to 8 by adopting hydrochloric acid, and then reacting for 10 hours at the temperature of 140 ℃ to obtain a reaction solution;
adjusting the pH value of the reaction solution to 7 by adopting hydrochloric acid, and then filtering to obtain a precipitate;
washing the precipitate to obtain a washed precipitate;
drying the washed precipitate at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 600 ℃ for 4h to obtain the lithiation modified rodlike ceramic filler;
wherein said Al is2O3The ratio of the mass of the nanowire to the volume of the lithium salt-containing ionized water is 1 g: 6 mL;
in the ionic water containing lithium acetate, the mass ratio of the lithium acetate to the ionic water containing lithium acetate is 1: 10.
in still another aspect of the present invention, there is additionally provided a method of preparing a composite solid electrolyte, the method comprising:
mixing the lithiation modified rodlike ceramic filler with a polymer to obtain a mixture;
mixing the mixture with an organic solvent, and stirring to obtain slurry;
pouring the slurry on a polytetrafluoroethylene plate, heating at the temperature of 55-65 ℃, and drying to obtain the composite solid electrolyte;
wherein the polymer is selected from one or more of polyethylene oxide, polypropylene carbonate, polyvinylidene fluoride, polyacrylonitrile, polypropylene oxide, polyethylene carbonate and polybutylene carbonate.
In some embodiments of the present invention, in the preparation method of the composite solid electrolyte, the mass ratio of the lithiated modified rod-like ceramic filler to the polymer is (1-10): 50;
the ratio of the mass of the polymer to the volume of the organic solvent is (2-3) g: 5 mL.
In some preferred embodiments of the present invention, in the method for preparing the composite solid electrolyte according to the present invention, the mass ratio of the lithiated modified rod-like ceramic filler to the polymer is 1: 10;
the ratio of the mass of the polymer to the volume of the organic solvent is 1 g: 2 mL.
In some embodiments of the present invention, in the method for preparing the composite solid electrolyte, the organic solvent is one or two selected from acetonitrile, dimethylformamide, dimethyl sulfone and N-methylpyrrolidone.
In another aspect of the invention, the invention further provides the application of the composite solid electrolyte obtained by the preparation method of the composite solid electrolyte in the preparation of a solid battery.
In some embodiments of the present invention, the method for preparing a composite solid electrolyte according to the present invention may be used for preparing a solid battery, wherein the solid battery may comprise: lithium iron phosphate batteries, lithium cobalt oxide batteries, and nickel cobalt manganese batteries.
One or more technical embodiments of the present invention have at least the following technical effects or advantages:
(1) according to the invention, the surface of the rod-shaped ceramic filler is subjected to lithiation treatment, so that Lewis acid sites on the surface of the rod-shaped ceramic filler are increased, the obtained lithiation modified rod-shaped ceramic filler combines the advantages of an inert filler and a fast ion conductor, the level of the fast ion conductor is achieved in performance, the environmental adaptability is improved, and the material cost is reduced. In addition, the lithiation modified rod-shaped ceramic filler provided by the invention can be applied to the preparation of a composite solid electrolyte, and can greatly improve the ionic conductivity of the composite solid electrolyte.
(2) In the preparation method of the lithiation modified rod-shaped ceramic filler provided by the invention, modification is directly carried out on the surface of the conventional rod-shaped ceramic filler, the process method is simple, the cost is low, and the mass production is easy.
(3) The composite solid electrolyte prepared by the lithiation modified rodlike ceramic filler provided by the invention can obviously improve the ionic conductivity of the composite solid electrolyte, so that the ionic conductivity is more than or equal to 4 multiplied by 10-4S/cm。
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 shows a scanning electron micrograph of a lithiated modified rod-shaped ceramic filler according to some embodiments of the present disclosure;
FIG. 2 shows a scanning electron micrograph of a composite solid electrolyte according to some embodiments of the present invention;
FIG. 3 illustrates an ionic conductivity impedance test curve for a composite solid state electrolyte according to some embodiments of the present invention;
FIG. 4 illustrates a potential window of a composite solid state electrolyte according to some embodiments of the invention;
fig. 5 illustrates electrical performance of a solid-state battery made from a composite solid-state electrolyte according to some embodiments of the present invention; and
fig. 6 shows a comparison of impedances of solid-state batteries prepared with composite solid-state electrolytes according to some embodiments of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
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.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
in one aspect of the present invention, there is provided a lithiated modified rod-shaped ceramic filler, wherein the lithiated modified rod-shaped ceramic filler comprises: a rod-like ceramic filler and lithium-containing oxide particles;
wherein the rod-shaped ceramic filler is selected from Al2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2One or more than two of nanowires or nanofibers;
the lithium-containing oxide particles include: one or more than two of Li-Al-O, Li-Ti-O, Li-Zr-O.
According to the invention, the surface of the rod-shaped ceramic filler is subjected to lithiation treatment, so that the Lewis acid sites on the surface of the rod-shaped ceramic filler are improved, and the obtained lithiation modified rod-shaped ceramic filler combines the advantages of an inert filler and a fast ion conductor, can be applied to the preparation of a composite solid electrolyte, and can improve the ionic conductivity of the composite solid electrolyte.
In some embodiments of the invention, the lithiated modified rod-like ceramic filler of the present invention has a diameter of 20 to 200 nm and a length of 1 to 50 μm.
Through a series of tests, the diameter of the lithiation modified rodlike ceramic filler is finally limited to be 20-200 nanometers, and the length of the lithiation modified rodlike ceramic filler is 1-50 micrometers, so that the lithiation modified rodlike ceramic filler is more suitable for preparing a composite solid electrolyte, and the ionic conductivity of the composite solid electrolyte is further improved.
In some preferred embodiments of the present invention, in the lithiated modified rod-like ceramic filler of the present invention, the diameter of the lithiated modified rod-like ceramic filler is 100 to 200 nm, and the length of the lithiated modified rod-like ceramic filler is 20 to 45 μm.
In order to further enhance the technical effect of the invention, the inventor limits the diameter of the lithiation modified rodlike ceramic filler to be 100-200 nanometers and the length to be 20-45 micrometers through further screening.
In some embodiments of the present invention, in the lithiated modified rod-like ceramic filler of the present invention, a mass ratio of the lithium-containing oxide particles to the lithiated modified rod-like ceramic filler is (1 to 15): 100.
the inventors have found that the mass ratio between the lithium oxide particles and the lithiated modified rod-like ceramic filler significantly affects the surface compactness of the subsequently prepared composite solid-state electrolyte and significantly affects the ionic conductivity of the composite solid-state electrolyte. Therefore, through a large number of experiments, the inventor finally defines the mass ratio of the lithium-containing oxide particles to the lithiation modified rod-shaped ceramic filler as (1-15): 100, so that the prepared composite solid electrolyte has smooth and compact surface and obviously improved ionic conductivity.
In some preferred embodiments of the present invention, in the lithiated modified rod-like ceramic filler of the present invention, a mass ratio of the lithium-containing oxide particles to the lithiated modified rod-like ceramic filler is (8 to 14): 100.
in order to further enhance the related technical effects, the inventor further screens to limit the mass ratio of the lithium-containing oxide particles to the lithiation modified rodlike ceramic filler to (8-14): 100.
in some preferred embodiments of the present invention, in the lithiated modified rod-shaped ceramic filler according to the present invention, the mass ratio of the lithium-containing oxide particles to the lithiated modified rod-shaped ceramic filler is 14.7: 100.
in order to achieve the best technical effect, the inventor finally defines the mass ratio of the lithium-containing oxide particles to the lithiation modified rod-shaped ceramic filler as (8-14): when the product is 100 hours, the beneficial effects of the product can be improved to the maximum extent by matching with other relevant process parameters.
In another aspect of the present invention, there is also provided a method for preparing the lithiated modified rod-like ceramic filler according to the present invention, including:
mixing the rod-shaped ceramic filler with ionic water containing lithium salt, and stirring to obtain a suspension;
adjusting the pH value of the suspension to 8-10, and then reacting at the temperature of 140-200 ℃ for 2-10 h to obtain a reaction solution;
adjusting the pH value of the reaction solution to 7-8, and then filtering to obtain a precipitate;
washing the precipitate to obtain a washed precipitate;
drying the washed precipitate at the temperature of 80-100 ℃ for 12-24 h, and then sintering at the temperature of 400-800 ℃ for 2-6 h to obtain the lithiation modified rodlike ceramic filler;
wherein the lithium salt is selected from one or more of lithium acetate, lithium nitrate and lithium chloride.
The lithiation modified rodlike ceramic filler provided by the invention is used for preparing the composite solid electrolyte, so that the ionic conductivity of the composite solid electrolyte can be obviously improved.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-like ceramic filler of the present invention, the ratio of the mass of the rod-like ceramic filler to the volume of the ionic water containing a lithium salt is (2-3) g: 15 mL. The inventor finally defines the ratio of the mass of the rod-shaped ceramic filler to the volume of the lithium salt-containing ionic water as (2-3) g: 15 mL.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, the ratio of the mass of the rod-shaped ceramic filler to the volume of the ionic water containing a lithium salt is 1 g: 6 mL. The inventors finally defined, for the purpose of the invention, a ratio of the mass of the rod-like ceramic filler to the volume of the ionic water containing a lithium salt of 1 g: 6 mL.
In some embodiments of the present invention, in the preparation method of the lithiated modified rod-like ceramic filler according to the present invention, in the ionic water containing a lithium salt, the mass ratio of the lithium salt to the ionic water containing a lithium salt is (2-3): 25. aiming at the purpose of the invention, through a large number of balance optimization tests, the mass ratio of the lithium salt to the ionic water containing the lithium salt is finally defined as (2-3): 25.
in some preferred embodiments of the present invention, in the preparation method of the lithiated modified rod-shaped ceramic filler according to the present invention, in the ionic water containing the lithium salt, the mass ratio of the lithium salt to the ionic water containing the lithium salt is 1: 10. based on the fact that the hydrolysis reaction rate of the lithium salt is in direct proportion to the concentration of the lithium salt, when the content of the lithium salt is high, the hydrolysis rate is increased, so that the lithium oxide particles become large and the surface becomes rough, and the lithium oxide particles are difficult to uniformly coat the surface of the rod-shaped oxide; if the concentration of lithium salt is low, the reaction rate is slow, and a long time is required to form the coating layer. Therefore, the present inventors finally defined the mass ratio of the lithium salt to the ionic water containing a lithium salt to be 1: 10.
in some preferred embodiments of the present invention, the method for preparing the lithiated modified rod-shaped ceramic filler according to the present invention comprises:
adding the Al2O3Mixing the nanowires with ionic water containing lithium acetate, and stirring to obtain a suspension;
adjusting the pH value of the suspension to 8 by adopting hydrochloric acid, and then reacting for 10 hours at the temperature of 140 ℃ to obtain a reaction solution;
adjusting the pH value of the reaction solution to 7 by adopting hydrochloric acid, and then filtering to obtain a precipitate;
washing the precipitate to obtain a washed precipitate;
drying the washed precipitate at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 600 ℃ for 4h to obtain the lithiation modified rodlike ceramic filler;
wherein said Al is2O3The ratio of the mass of the nanowire to the volume of the lithium salt-containing ionized water is 1 g: 6 mL;
in the ionic water containing lithium acetate, the mass ratio of the lithium acetate to the ionic water containing lithium acetate is 1: 10.
the inventor finally confirms an optimized technical scheme through a large number of experiments, so that the obtained lithiation modified rodlike ceramic filler maximally combines the advantages of inert fillers and fast ion conductors, the ionic conductivity of the composite solid electrolyte can be maximally improved, and the ionic conductivity reaches 4.7 multiplied by 10-4And more than S/cm.
In still another aspect of the present invention, there is additionally provided a method of preparing a composite solid electrolyte, the method comprising:
mixing the lithiation modified rodlike ceramic filler with a polymer to obtain a mixture;
mixing the mixture with an organic solvent, and stirring to obtain slurry;
pouring the slurry on a polytetrafluoroethylene plate, heating at the temperature of 55-65 ℃, and drying to obtain the composite solid electrolyte;
wherein the polymer is selected from one or more of polyethylene oxide, polypropylene carbonate, polyvinylidene fluoride, polyacrylonitrile, polypropylene oxide, polyethylene carbonate and polybutylene carbonate.
According to the invention, the lithiation modified rodlike ceramic filler is mixed with the polymer, so that Lewis acid-base reaction is easier to occur among the ceramic filler, the polymer and the lithium salt.
In some embodiments of the present invention, in the preparation method of the composite solid electrolyte, the mass ratio of the lithiated modified rod-like ceramic filler to the polymer is (1-10): 50;
the ratio of the mass of the polymer to the volume of the organic solvent is (2-3) g: 5 mL.
Aiming at the purpose of the invention, the mass ratio of the lithiation modified rodlike ceramic filler to the polymer is finally limited to (1-10): 50 and a ratio of the mass of the polymer to the volume of the organic solvent defined as (2-3) g: 5 mL.
In some preferred embodiments of the present invention, in the method for preparing the composite solid electrolyte, the mass ratio of the lithiated modified rod-like ceramic filler to the polymer is 1: 10;
the ratio of the mass of the polymer to the volume of the organic solvent is 1 g: 2 mL.
Aiming at the invention purpose, through a large amount of balance optimization experiments, in order to realize the optimized technical effect, the mass ratio of the lithiation modified rodlike ceramic filler to the polymer is defined as 1: 10 and a ratio of the mass of the polymer to the volume of the organic solvent defined as 1 g: 2 mL.
A lithiated modified rod-shaped ceramic filler, a method for preparing the same, and applications thereof, which are described herein, will be described in detail with reference to examples, comparative examples, and experimental data.
Example 1: the lithiation modified rod-shaped ceramic filler and the composite solid electrolyte are prepared
In this embodiment, the preparation method of the lithiation-modified rod-like ceramic filler includes:
(1) adding TiO into the mixture2Dispersing the nano-fibers in deionized water containing lithium acetate, and stirring to form uniform suspension;
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8, placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 2h at the temperature of 140 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7, and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (3) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 400 ℃ for 2h to obtain the lithiation modified rod-shaped ceramic filler.
In this embodiment, the preparation method of the composite solid electrolyte includes:
(a) mixing the prepared lithiation modified rodlike ceramic filler with polypropylene carbonate to obtain a mixture;
(b) mixing the mixture obtained in the step (a) with dimethylformamide, and stirring to obtain slurry;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 55 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this example was about 20 nanometers in diameter and about 1 micrometer in length. Wherein, in the lithiation modified rod-shaped ceramic filler, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler, and the lithium-containing oxide particles are detected as Li4Ti5O12The Li4Ti5O12The mass ratio of the particles to the lithiated modified rodlike ceramic filler is 1: 100.
the composite solid electrolyte prepared by the embodiment has smooth and compact surface and the ionic conductivity of 3.9 multiplied by 10-4S/cm, potential window of 4.6V. The impedance of the battery prepared by the composite solid electrolyte is obviously reduced, and the composite solid electrolyte is particularly suitable for lithium iron phosphate batteries, lithium cobaltate batteries and nickel cobalt manganese batteries.
Example 2: the lithiation modified rod-shaped ceramic filler and the composite solid electrolyte are prepared
In this embodiment, the preparation method of the lithiation-modified rod-like ceramic filler includes:
(1) mixing Al2O3The nanowires are dispersed in a solvent containingStirring lithium chloride in deionized water to form uniform suspension; wherein, Al2O3The ratio of the mass of the nanowires to the volume of the ionized water containing lithium chloride was 2 g: 15 mL; in the ionized water containing lithium chloride, the mass ratio of the lithium chloride to the ionized water containing lithium chloride is 2: 25.
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 10h at 200 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 8 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (3) drying the precipitate obtained in the step (4) at the temperature of 100 ℃ for 24h, and then sintering at the temperature of 800 ℃ for 6h to obtain the lithiation modified rod-shaped ceramic filler.
In this embodiment, the preparation method of the composite solid electrolyte includes:
(a) mixing the lithiation modified rodlike ceramic filler prepared above with polyethylene oxide to obtain a mixture; wherein the mass ratio of the lithiation modified rodlike ceramic filler to the polyethylene oxide is 1: 50;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry; wherein the ratio of the mass of the polymer to the volume of acetonitrile is 2 g: 5 mL;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 60 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this example was about 200 nm in diameter and about 50 microns in length. Wherein, in the lithiation modified rod-shaped ceramic filler, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler, and the lithium-containing oxide particles are detected as LiAlO2The LiAlO2The mass ratio of the particles to the lithiated modified rodlike ceramic filler is 3: 20.
composite solid electrolyte prepared in this example, TableThe surface is smooth and dense, as shown in fig. 2. The ionic conductivity reaches 5 x 10-4S/cm, potential window 4.7V, as shown in FIGS. 3 and 4. The impedance of the battery prepared by using the composite solid electrolyte is obviously reduced, the battery is particularly suitable for lithium iron phosphate batteries, lithium cobaltate batteries and nickel cobalt manganese batteries, and the battery shows good rate performance in the nickel cobalt manganese batteries, as shown in fig. 5.
Example 3: the lithiation modified rod-shaped ceramic filler and the composite solid electrolyte are prepared
In this embodiment, the preparation method of the lithiation-modified rod-like ceramic filler includes:
(1) mixing Al2O3Nanowire and ZrO2Dispersing the nanowires in deionized water containing lithium nitrate, and stirring to obtain a uniform suspension; wherein, Al2O3Nanowire and ZrO2The ratio of the total mass of the nanowires to the volume of the ionized water containing lithium nitrate was 1 g: 5 mL; in the ionized water containing lithium nitrate, the mass ratio of the lithium nitrate to the ionized water containing lithium nitrate is 3: 25.
(2) adjusting the pH value of the suspension obtained in the step (1) to 10, placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 9h at 150 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 8, and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 4 times;
(5) and (3) drying the precipitate obtained in the step (4) at the temperature of 90 ℃ for 20h, and then sintering at the temperature of 500 ℃ for 4h to obtain the lithiation modified rod-shaped ceramic filler.
In this embodiment, the preparation method of the composite solid electrolyte includes:
(a) mixing the prepared lithiation modified rod-shaped ceramic filler with polyvinylidene fluoride to obtain a mixture; wherein the mass ratio of the lithiation modified rodlike ceramic filler to the polyvinylidene fluoride is 1: 5;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry; wherein the ratio of the mass of the polymer to the volume of acetonitrile is 3 g: 5 mL;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 65 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this example was about 100 nanometers in diameter and about 45 micrometers in length. Wherein, in the lithiation modified rod-shaped ceramic filler, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler, and the lithium-containing oxide particles are detected as LiAlO2And Li2ZrO3The mass ratio of the mixed particles to the lithiated modified rod-like ceramic filler is 2: 25.
the composite solid electrolyte prepared by the embodiment has smooth and compact surface and the ionic conductivity of 4.5 multiplied by 10-4S/cm, potential window of 4.7V. The impedance of the battery prepared by the composite solid electrolyte is obviously reduced, and the composite solid electrolyte is particularly suitable for lithium iron phosphate batteries, lithium cobaltate batteries and nickel cobalt manganese batteries.
Example 4: the lithiation modified rod-shaped ceramic filler and the composite solid electrolyte are prepared
In this embodiment, the preparation method of the lithiation-modified rod-like ceramic filler includes:
(1) ZrO 2 is mixed with2Dispersing the nanowires in deionized water containing lithium acetate, and stirring to obtain a uniform suspension; wherein, ZrO2The ratio of the mass of the nanowires to the volume of the ionized water containing lithium acetate was 2 g: 15 mL; in the ionic water containing lithium acetate, the mass ratio of the lithium acetate to the ionic water containing the lithium acetate is 2: 25.
(2) adjusting the pH value of the suspension obtained in the step (1) to 10, placing the suspension in a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 9h at 180 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7, and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 4 times;
(5) and (3) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 20h, and then sintering at the temperature of 400 ℃ for 6h to obtain the lithiation modified rod-shaped ceramic filler.
In this embodiment, the preparation method of the composite solid electrolyte includes:
(a) mixing the prepared lithiation modified rodlike ceramic filler with polyacrylonitrile to obtain a mixture; wherein the mass ratio of the lithiation modified rodlike ceramic filler to the polyacrylonitrile is 3: 25;
(b) mixing the mixture obtained in the step (a) with dimethylformamide, and stirring to obtain slurry; wherein the ratio of the mass of the polymer to the volume of dimethylformamide is 2.5 g: 5 mL;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 65 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this example was about 200 nm in diameter and about 20 microns in length. Wherein, in the lithiation modified rod-shaped ceramic filler, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler, and the lithium-containing oxide particles are detected as Li2ZrO3The Li2ZrO3The mass ratio of the particles to the lithiated modified rodlike ceramic filler is 7: 50.
the composite solid electrolyte prepared by the embodiment has smooth and compact surface and the ionic conductivity of 4.5 multiplied by 10-4S/cm, potential window of 4.7V. The impedance of the battery prepared by the composite solid electrolyte is obviously reduced, and the composite solid electrolyte is particularly suitable for lithium iron phosphate batteries, lithium cobaltate batteries and nickel cobalt manganese batteries.
Example 5: the lithiation modified rod-shaped ceramic filler and the composite solid electrolyte are prepared
In this embodiment, the preparation method of the lithiation-modified rod-like ceramic filler includes:
(1) mixing Al2O3Dispersing the nanowires in deionized water containing lithium acetate, and stirring to obtain a uniform suspension; wherein, Al2O3The ratio of the mass of the nanowires to the volume of the ionized water containing lithium acetate was 1 g: 6 mL; in the ionized water containing lithium acetate, the lithium acetate and the ions containing the lithium acetateThe mass ratio of water is 1: 10.
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 10h at 140 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (3) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 600 ℃ for 4h to obtain the lithiation modified rod-shaped ceramic filler.
In this embodiment, the preparation method of the composite solid electrolyte includes:
(a) mixing the prepared lithiation modified rodlike ceramic filler with polyacrylonitrile to obtain a mixture; wherein the mass ratio of the lithiation modified rodlike ceramic filler to the polyacrylonitrile is 1: 10;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry; wherein the ratio of the mass of the polymer to the volume of acetonitrile is 1 g: 2 mL;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 65 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this example was about 150 nm in diameter and about 45 microns in length. Wherein, in the lithiation modified rod-shaped ceramic filler, the lithium-containing oxide particles are coated on the surface of the rod-shaped ceramic filler, and the lithium-containing oxide particles are detected as LiAl5O8The LiAl5O8The mass ratio of the particles to the lithiated modified rodlike ceramic filler is 14.7: 100.
the composite solid electrolyte prepared by the embodiment has smooth and compact surface and the ionic conductivity of 4.7 multiplied by 10-4S/cm, potential window of 4.7V. The impedance of the battery prepared by the composite solid electrolyte is obviously reduced, and the composite solid electrolyte is particularly suitable for lithium iron phosphate batteries, lithium cobalt oxide batteries and nickel cobalt manganese batteries。
Comparative example 1: preparation of rod-shaped ceramic filler and composite solid electrolyte
In this comparative example, a rod-shaped ceramic filler was prepared by a method comprising:
(1) mixing SiO2Dispersing the nano-fibers in deionized water containing lithium acetate, and stirring to form uniform suspension;
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8, placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 2h at the temperature of 140 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7, and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (4) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 400 ℃ for 2h to obtain the rod-shaped ceramic filler.
In this comparative example, the method of preparing the solid electrolyte included:
(a) mixing the prepared rod-shaped ceramic filler with polymethyl methacrylate to obtain a mixture;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 55 ℃, and drying to obtain the composite solid electrolyte.
The lithiated modified rod-like ceramic filler prepared in this comparative example was about 250 nm in diameter and about 1 μm in length.
The ionic conductivity of the composite solid electrolyte prepared by the comparative example reaches 3.2 multiplied by 10-4S/cm, potential window of 4.4V.
Comparative example 2: preparation of rod-shaped ceramic filler and composite solid electrolyte
In this comparative example, a rod-shaped ceramic filler was prepared by a method comprising:
(1) SnO2Dispersing the nano-fiber in deionized water containing lithium nitrate, and stirring to form uniform suspensionLiquid;
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8, placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 2h at the temperature of 140 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7, and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (4) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 400 ℃ for 2h to obtain the rod-shaped ceramic filler.
In this comparative example, the method of preparing the solid electrolyte included:
(a) mixing the prepared lithiation modified rod-shaped ceramic filler with a polyvinylidene fluoride-hexafluoropropylene copolymer to obtain a mixture;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 55 ℃, and drying to obtain the solid electrolyte.
The rod-shaped ceramic filler prepared in this comparative example had a diameter of about 18 nm and a length of about 55 μm.
The ionic conductivity of the composite solid electrolyte prepared by the comparative example reaches 3.1 multiplied by 10-4S/cm, potential window of 4.5V.
Comparative example 3: preparation of rod-shaped ceramic filler and composite solid electrolyte
In this comparative example, a rod-shaped ceramic filler was prepared by a method comprising:
(1) mixing Al2O3Dispersing the nanowires in deionized water containing lithium acetate, and stirring to obtain a uniform suspension; wherein, Al2O3The ratio of the mass of the nanowires to the volume of the ionized water containing lithium acetate was 4 g: 15 mL; in the ionized water containing the lithium acetate, the mass ratio of the lithium acetate to the ionized water containing the lithium acetate is 4: 25.
(2) adjusting the pH value of the suspension obtained in the step (1) to be 8 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), placing the suspension into a reaction kettle with the volume of 100mL, and carrying out hydrothermal reaction for 10h at 140 ℃ to obtain a reaction solution;
(3) adjusting the pH value of the reaction solution obtained in the step (2) to 7 by adopting hydrochloric acid (the mass fraction of HCl is about 37%), and filtering to obtain a precipitate;
(4) washing the precipitate obtained in the step (3) for 3 times;
(5) and (4) drying the precipitate obtained in the step (4) at the temperature of 80 ℃ for 12h, and then sintering at the temperature of 600 ℃ for 4h to obtain the rod-shaped ceramic filler.
In this comparative example, the method of preparing the solid electrolyte included:
(a) mixing the prepared rod-shaped ceramic filler with polyacrylonitrile to obtain a mixture; wherein the mass ratio of the rod-shaped ceramic filler to the polyacrylonitrile is 1: 10;
(b) mixing the mixture obtained in the step (a) with acetonitrile, and stirring to obtain slurry; wherein the ratio of the mass of the polymer to the volume of acetonitrile is 1 g: 2 mL;
(c) and (c) pouring the slurry obtained in the step (b) on a polytetrafluoroethylene plate, heating at the temperature of 65 ℃, and drying to obtain the solid electrolyte.
The rod-shaped ceramic filler prepared in this comparative example had a diameter of about 250 nm and a length of about 45 μm.
The composite solid electrolyte prepared by the comparative example has smooth and compact surface and the ionic conductivity reaches 3.6 multiplied by 10-4S/cm, potential window of 4.7V.
As can be seen from the comparison between examples 1 to 5 of the present invention and comparative examples 1 to 3, the following:
(1) the invention is through the reaction of Al2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2The surface of the nano wire or the nano fiber is lithiated, so that the Lewis acid sites on the surface of the rod-shaped ceramic filler are improved, the advantages of the inert filler and the fast ion conductor are combined, the performance of the rod-shaped ceramic filler reaches the level of the fast ion conductor, the environmental adaptability is improved, and the material cost is reduced. In addition, the lithiation modified rod-shaped ceramic filler provided by the invention can be applied to the preparation of composite solid electrolytes,the ionic conductivity of the composite solid electrolyte can be greatly improved.
(2) The inventor limits the diameter of the lithiation modified rodlike ceramic filler to be 20-200 nanometers, the length of the lithiation modified rodlike ceramic filler to be 1-50 micrometers, and further preferably the diameter of the lithiation modified rodlike ceramic filler to be 100-200 nanometers and the length of the lithiation modified rodlike ceramic filler to be 20-45 micrometers, so that the lithiation modified rodlike ceramic filler is more suitable for preparing a composite solid electrolyte, and the ionic conductivity of the composite solid electrolyte is further improved.
(3) The present inventors have defined that the ratio of the mass of the rod-like ceramic filler to the volume of the ionic water containing a lithium salt is (2 to 3) g: 15mL, and preferably 1 g: 6mL, so that the filler is uniformly dispersed in the aqueous solution, and the agglomeration is reduced.
(4) The present inventors define the lithium salt-containing ionized water, wherein the mass ratio of the lithium salt to the lithium salt-containing ionized water is (2-3): 25, and preferably 1: 10 so that the lithium salt is uniformly deposited and reacted on the surface of the ceramic filler.
Furthermore, in the present invention: fig. 1 shows a scanning electron micrograph of a lithiated modified rod-shaped ceramic filler according to some embodiments of the present disclosure, illustrating that the lithiated modified rod-shaped ceramic filler disperses well and maintains a large aspect ratio. Fig. 2 shows a scanning electron micrograph of a composite solid electrolyte according to some embodiments of the present invention, illustrating the uniform density, smooth surface and uniform filler distribution of the formed electrolyte. FIG. 3 shows ion conductivity impedance test curves for composite solid electrolytes illustrating the addition of lithiated modified rod-shaped ceramic fillers to achieve 5X 10 ion conductivity of the electrolyte according to some embodiments of the present invention-4S/cm. Fig. 4 shows the potential window of a composite solid electrolyte according to some embodiments of the present invention, illustrating the addition of lithiated modified rod-like ceramic fillers to achieve a potential window of the electrolyte above 4.7V. Fig. 5 shows the electrical performance of a solid-state battery prepared from a composite solid-state electrolyte according to some embodiments of the present invention, illustrating that the rate performance of the battery is good with an electrolyte that incorporates lithiated modified rod-like ceramic fillers, which is suitable for a solid-state battery. FIG. 6 illustrates a solid-state battery fabricated with a composite solid-state electrolyte according to some embodiments of the inventionImpedance comparison, which illustrates that electrolyte with lithiated modified rod-shaped ceramic fillers added, makes the impedance of the cell less than that of the cell made up of unmodified electrolyte.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred comparative examples of the present invention have been described, additional variations and modifications in those comparative examples may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred comparative examples and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A lithiated modified rod-shaped ceramic filler, comprising: a rod-like ceramic filler and lithium-containing oxide particles;
wherein the rod-shaped ceramic filler is selected from Al2O3Nanowires or nanofibers, TiO2Nanowires or nanofibers, ZrO2One or more than two of nanowires or nanofibers;
the lithium-containing oxide particles include: one or more than two of Li-Al-O, Li-Ti-O, Li-Zr-O.
2. The lithiated modified rod-like ceramic filler according to claim 1, wherein the lithiated modified rod-like ceramic filler has a diameter of 20 to 200 nm and a length of 1 to 50 μm.
3. The lithiated modified rod-like ceramic filler according to claim 1 or 2, wherein the mass ratio of the lithium-containing oxide particles to the lithiated modified rod-like ceramic filler is (1 to 15): 100.
4. a method of preparing a lithiated modified rod-shaped ceramic filler according to any one of claims 1 to 3, the method comprising:
mixing the rod-shaped ceramic filler with ionic water containing lithium salt, and stirring to obtain a suspension;
adjusting the pH value of the suspension to 8-10, and then reacting at the temperature of 140-200 ℃ for 2-10 h to obtain a reaction solution;
adjusting the pH value of the reaction solution to 7-8, and then filtering to obtain a precipitate;
washing the precipitate to obtain a washed precipitate;
drying the washed precipitate at the temperature of 80-100 ℃ for 12-24 h, and then sintering at the temperature of 400-800 ℃ for 2-6 h to obtain the lithiation modified rodlike ceramic filler;
wherein the lithium salt is selected from one or more of lithium acetate, lithium nitrate and lithium chloride.
5. The method for preparing the lithiated modified rod-like ceramic filler according to claim 4, wherein the ratio of the mass of the rod-like ceramic filler to the volume of the lithium salt-containing ionic water is (2 to 3) g: 15 mL.
6. The method of preparing a lithiated modified rod-like ceramic filler according to claim 4, wherein the ratio of the mass of the rod-like ceramic filler to the volume of the ionized water containing a lithium salt is 1 g: 6 mL.
7. The method for preparing the lithiated modified rod-like ceramic filler according to claim 4 or 5, wherein the mass ratio of the lithium salt to the ionic water containing the lithium salt is (2-3): 25.
8. a method of preparing a composite solid electrolyte, the method comprising:
mixing a lithiated modified rod-shaped ceramic filler according to any one of claims 1 to 3 or a lithiated modified rod-shaped ceramic filler obtained by the method for preparing a lithiated modified rod-shaped ceramic filler according to any one of claims 4 to 7 with a polymer to obtain a mixture;
mixing the mixture with an organic solvent, and stirring to obtain slurry;
pouring the slurry on a polytetrafluoroethylene plate, heating at the temperature of 55-65 ℃, and drying to obtain the composite solid electrolyte;
wherein the polymer is selected from one or more of polyethylene oxide, polypropylene carbonate, polyvinylidene fluoride, polyacrylonitrile, polypropylene oxide, polyethylene carbonate and polybutylene carbonate.
9. The preparation method of the composite solid electrolyte according to claim 8, wherein the mass ratio of the lithiated modified rod-like ceramic filler to the polymer is (1-10): 50;
the ratio of the mass of the polymer to the volume of the organic solvent is (2-3) g: 5 mL.
10. Use of the composite solid electrolyte obtained by the method for producing a composite solid electrolyte according to claim 8 or 9 for producing a solid-state battery.
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