A nanoscale fluoride solid-state electrolyte material, a preparation method and application thereof

Abstract

This invention relates to a nanoscale fluoride solid electrolyte material, its preparation method, and its application. The method includes: taking a non-fluorine-containing source according to the molar ratio of each element in the fluoride solid electrolyte material, and grinding it with a first solvent in a first grinding device to obtain a first mixed slurry; spray-drying the first mixed slurry to obtain a first precursor; sintering the first precursor in a first sintering device to obtain a pre-sintered precursor; grinding the pre-sintered precursor and a second solvent in a second grinding device to obtain a second mixed slurry; grinding a fluorine source and a third solvent in a third grinding device to obtain a fluorine-containing slurry; adding the second mixed slurry to the third grinding device and mixing to obtain a third mixed slurry; spray-drying the third mixed slurry to obtain a second precursor; sintering the second precursor and then pulverizing it to obtain the nanoscale fluoride solid electrolyte material.

Description

Technical Field

[0001] This invention relates to the field of materials technology, and in particular to a nanoscale fluoride solid electrolyte, its preparation method, and its application. Background Technology

[0002] With the rapid development of electric vehicles and portable electronic devices, the demand for batteries with high energy density and high safety is increasing. Lithium-ion batteries are widely used in electronic products and electric vehicles due to their high energy density, long cycle life, and environmental friendliness. Solid electrolyte materials, with their high safety, non-flammability, and wide electrochemical window, have become an important component of lithium-ion batteries, among which fluoride solid electrolyte materials are one type.

[0003] Currently, fluoride solid electrolytes on the market include micron-sized, submicron-sized, and nano-sized products. They are all prepared by post-processing of finished products using traditional solid-phase methods, sol-gel methods, and mechanical ball milling methods. These submicron-sized and nano-sized process routes have problems such as high energy consumption from high-temperature calcination and low material density.

[0004] Therefore, how to avoid the high calcination temperature in the synthesis stage and the high energy consumption in the pulverization stage of fluoride solid electrolytes is a technical problem that urgently needs to be solved. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing a nanoscale fluoride solid electrolyte, its preparation method, and its applications.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing nanoscale fluoride solid electrolyte materials, the preparation method comprising:

[0007] A non-fluorine-containing source is taken according to the molar ratio of each element in the fluoride solid electrolyte material, and is put into the first grinding equipment with the first solvent for the first grinding process to obtain the first mixed slurry; the particle size Dv100 of the first mixed slurry is less than 1000nm;

[0008] The first mixed slurry was subjected to a first spray drying treatment to obtain a first precursor.

[0009] The first precursor is placed in the first sintering equipment for the first sintering to obtain a pre-sintered precursor.

[0010] The pre-sintered precursor and the second solvent are subjected to a second grinding process in a second grinding equipment to obtain a second mixed slurry; the particle size Dv50 of the second mixed slurry is 10nm-1000nm;

[0011] The fluorine source and the third solvent are subjected to a third grinding process in a third grinding device to obtain a fluorine-containing slurry; the particle size Dv50 of the fluorine-containing slurry is 10nm-1000nm.

[0012] The second mixed slurry is fed into the third grinding equipment and mixed to obtain the third mixed slurry;

[0013] The third mixed slurry is subjected to a second spray drying treatment to obtain the second precursor;

[0014] The second precursor is placed in a second sintering device for a second sintering, and then pulverized to obtain the nano-scale fluoride solid electrolyte material.

[0015] Preferably, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate; the lanthanum source is one or more of lanthanum trioxide, lanthanum carbonate, lanthanum nitrate, lanthanum hydroxide, and lanthanum fluoride; the fluorine source is one or more of ammonium fluoride, lithium fluoride, lanthanum fluoride, and aluminum fluoride; and the fluoride solid electrolyte is a fluoride solid electrolyte LLMOF, wherein the general chemical formula of LLMOF is Li x La y M1 z M2 w M3 u O6F, M1 is a tetravalent cation, M2 is a pentavalent cation, M3 is a hexavalent cation, and 1 < x + 3y ≤ 5, 0 < x ≤ 2, 1 / 3 < y < 5 / 3, 0 ≤ z ≤ 2, 0 ≤ w ≤ 2, 0 ≤ u ≤ 2, z + w + u = 2.

[0016] Preferably, the first solvent is one or more selected from deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone.

[0017] The first grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, and a high-energy ball mill; the grinding media for the first grinding treatment is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm, and the grinding time is 1 hour-24 hours;

[0018] The solid content of the first mixed slurry is 5%-60%;

[0019] The equipment for the first spray drying process includes an open spray dryer or a closed spray dryer; the inlet temperature of the equipment is 150℃-260℃, and the outlet temperature is 60℃-150℃.

[0020] Preferably, the first sintering equipment is any one of a box furnace, tube furnace, pusher furnace, roller kiln, or rotary furnace; the specific conditions for the first sintering are: heating to 200℃-600℃ at a heating rate of 1℃ / min-20℃ / min, and holding at that temperature for 1 hour-8 hours.

[0021] Preferably, the second solvent is one or more selected from deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone.

[0022] The second grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, or a high-energy ball mill;

[0023] The grinding media for the second grinding process is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm; and the grinding time is 1 hour-24 hours.

[0024] Preferably, the third solvent is one or more selected from deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone.

[0025] The third grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, or a high-energy ball mill.

[0026] The grinding media for the third grinding process is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm; and the grinding time is 1 hour-24 hours.

[0027] The solid content of the fluorinated slurry is 1%-60%; the particle size ratio (Dv50) of the fluorinated slurry to that of the second mixed slurry is [0.01-0.5]:1.

[0028] Preferably, the equipment for the second spray drying process includes an open spray dryer or a closed spray dryer; the inlet temperature of the equipment is 150℃-260℃, and the outlet temperature is 60℃-150℃.

[0029] The second sintering equipment is any one of a box furnace, tube furnace, pusher furnace, roller kiln, or rotary furnace; the specific conditions for the second sintering are: under an inert atmosphere, the temperature is raised to 700℃-1100℃ at a heating rate of 1℃ / min-10℃ / min, and held for 1 hour-12 hours, wherein the inert atmosphere includes one or more combinations of nitrogen and argon.

[0030] Preferably, the equipment for the pulverization process is a fluidized bed jet mill or a flat jet mill, the pressure of the compressed air is between 2MPa and 5MPa, and the dew point of the compressed air is less than -20℃.

[0031] In a second aspect, the present invention provides a nanoscale fluoride solid electrolyte material, wherein the nanoscale fluoride solid electrolyte material is prepared by any of the preparation methods described in the first aspect above.

[0032] Thirdly, the present invention provides a battery comprising the nanoscale fluoride solid electrolyte material described in the second aspect.

[0033] The method for preparing nanoscale fluoride solid electrolyte materials provided in this invention involves the following steps: During the first grinding process, the collision and shear force between the grinding media and the raw materials cause the chemical bonds on the surface of the raw material particles to break, generating unsaturated dangling bonds. This enhances the surface activity of the particles and triggers the interconnection of the dangling bonds generated during grinding, resulting in a uniformly mixed, pre-bonded nanoscale slurry. During the first spray drying process, the solvent in the first mixed slurry is rapidly evaporated, and the raw materials achieve a pre-assembled state between particles through the interconnected dangling bonds. Subsequently, the first sintering process promotes the reaction and bonding of the raw materials. Simultaneously, the nanoscale particles and surface dangling bonds increase the surface activity of the particles, significantly improving the particle reaction diffusion rate. This accelerates the sintering rate, reduces the temperature and time of the raw material reaction, and solves the problem of high energy consumption in high-temperature calcination. The pre-sintering precursor and the fluorine source have different particle sizes. The smaller particle size of the fluorine source allows for uniform distribution within the pre-sintering precursor. After the second spray drying, the fluorine source is evenly distributed across the surface and interstices of the pre-sintering precursor. During the second sintering process, the fluorine source, with its lower melting point, preferentially melts to form a liquid phase, filling the gaps between particles, thus reducing the material's porosity and increasing its density. Because the raw materials are all nano-sized particles reacting, they are easier to break during the pulverization process, avoiding the energy consumption associated with hard crushing from micrometer-sized particles to nano-powder. Attached Figure Description

[0034] Figure 1 This is a flowchart illustrating the preparation method of nanoscale fluoride solid electrolyte material provided in this embodiment of the invention.

[0035] Figure 2Comparison of X-ray diffraction (XRD) images of fluoride solid electrolyte materials in Examples 1-2 and Comparative Examples 1-3 provided for embodiments of the present invention. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0037] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0038] This invention provides a method for preparing nanoscale fluoride solid electrolyte materials, the process of which is as follows: Figure 1 As shown, it includes the following steps:

[0039] Step 110: Take a non-fluorine-containing source according to the molar ratio of each element in the fluoride solid electrolyte material, and put it into the first grinding equipment with the first solvent for the first grinding treatment to obtain the first mixed slurry;

[0040] Among them, the general chemical formula of fluoride solid electrolyte (LLMOF) is Li x La y M1 z M2 w M3 u O6F, M1 is a tetravalent cation, M2 is a pentavalent cation, M3 is a hexavalent cation, and 1 < x + 3y < 5, 0 < x ≤ 2, 1 / 3 < y < 5 / 3, 0 ≤ z ≤ 2, 0 ≤ w ≤ 2, 0 ≤ u ≤ 2, z + w + u = 2.

[0041] In the alternative schemes, M1, M2, and M3 in LLMOF have at least two components, that is, two of z, w, and u are not simultaneously zero.

[0042] Wherein, M1 can be one or more of Zr, Ti, Hf, Si, Ge, and Sn. M2 can be one or more of Nb, Sb, Bi, V, and Ta. M3 can be one or more of W, Cr, Mo, and Mn.

[0043] The lithium source can be one or more of lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate. The lanthanum source can be one or more of lanthanum trioxide, lanthanum carbonate, lanthanum nitrate, lanthanum hydroxide, and lanthanum fluoride. The M source is an oxide of M1, M2, or M3.

[0044] The first solvent can be one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone.

[0045] The first grinding equipment can be one or more of the following: a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, and a high-energy ball mill. The grinding media for the first grinding process can be one or more of the following: glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads. The diameter of the grinding media can be one or more of the following: 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm. The grinding speed can be 500rpm-3000rpm, preferably 1500rpm-2000rpm, and the grinding time can be 1 hour-24 hours, preferably 4 hours.

[0046] During this process, the collisions and shear forces between the grinding media and raw materials such as the lithium source cause the chemical bonds on the surface of the raw material particles to break, generating unsaturated dangling bonds. This enhances the surface activity of the particles and triggers the interconnection of the dangling bonds generated during grinding, thus obtaining a preliminarily bonded nanoscale slurry, namely the first mixed slurry. The solid content of the first mixed slurry can be 5%-60%, preferably 20%-40%. The particle size Dv100 of the first mixed slurry is less than 1000 nm.

[0047] Step 120: Perform a first spray drying treatment on the first mixed slurry to obtain the first precursor;

[0048] Specifically, the equipment for the first spray drying process can include an open spray dryer or a closed spray dryer. The inlet temperature of the equipment can be 150℃-260℃, preferably 220℃-240℃, and the outlet temperature can be 60℃-150℃, preferably 120℃.

[0049] During this process, the solvent in the first mixed slurry evaporates rapidly, and the raw materials reach a pre-assembled state between particles through interconnected dangling bonds.

[0050] Step 130: The first precursor is placed in the first sintering equipment for the first sintering to obtain the pre-sintered precursor;

[0051] Specifically, the first sintering equipment can be any one of a box furnace, tube furnace, pusher furnace, roller kiln, or rotary furnace. The specific conditions for the first sintering are: heating to 200℃-600℃ at a heating rate of 1℃ / min-20℃ / min, holding at that temperature for 1 hour-8 hours, preferably heating to 500℃-600℃ at a rate of 2℃ / min-5℃ / min, and holding at that temperature for 4 hours-6 hours.

[0052] During the sintering process, the reaction and bonding of various raw materials are promoted. At the same time, the nano-sized particles and surface dangling bonds can increase the surface activity of the particles, significantly improving the particle reaction diffusion rate, thereby accelerating the sintering rate, reducing the temperature and time of the raw material reaction, and solving the problem of high energy consumption in high-temperature calcination.

[0053] Step 140: The pre-sintered precursor and the second solvent are subjected to a second grinding process in a second grinding device to obtain a second mixed slurry;

[0054] Specifically, the second solvent can be one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone. The second grinding equipment can be any one of a horizontal sand mill, vertical sand mill, planetary mixer, vertical mixing tank, or high-energy ball mill. The grinding media for the second grinding process can be one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads. The diameter of the grinding media can be one or more of 0.03 mm, 0.05 mm, 0.1 mm, 0.3 mm, 0.5 mm, 0.8 mm, and 1 mm. The grinding speed can be 500 rpm to 3000 rpm, preferably 1500 rpm to 2000 rpm, and the grinding time can be 1 hour to 24 hours, preferably 2.5 hours to 4 hours.

[0055] The particle size Dv50 of the second mixed slurry is 10nm-1000nm.

[0056] Step 150: The fluorine source and the third solvent are subjected to a third grinding process in a third grinding device to obtain a fluorine-containing slurry;

[0057] The fluorine source can be one or more of ammonium fluoride, lithium fluoride, lanthanum fluoride, and aluminum fluoride. The third solvent can be one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone. The third grinding equipment can be any one of a horizontal sand mill, vertical sand mill, planetary mixer, vertical mixing tank, or high-energy ball mill. The grinding media for the third grinding process can be one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads. The diameter of the grinding media can be one or more of 0.03 mm, 0.05 mm, 0.1 mm, 0.3 mm, 0.5 mm, 0.8 mm, and 1 mm. The grinding speed can be 500 rpm to 3000 rpm, preferably 2000 rpm, and the grinding time can be 1 hour to 24 hours, preferably 4 hours to 5 hours.

[0058] The particle size Dv50 of the fluorinated slurry is 10nm-1000nm. The solid content of the fluorinated slurry is specifically 1%-60%, preferably 20%. The particle size Dv50 of the fluorinated slurry and the second mixed slurry is [0.01-0.5]:1. The smaller particle size of the fluorinated slurry can fill the interparticle gaps, increasing the particle density after spraying.

[0059] Step 160: The second mixed slurry is fed into the third grinding equipment and mixed to obtain the third mixed slurry;

[0060] Specifically, in this process, the pre-sintered precursor in the second mixed slurry has a different particle size than the fluorine source in the fluorine-containing slurry. The smaller particle size of the fluorine source can be evenly distributed in the pre-sintered precursor.

[0061] Step 170: The third mixed slurry is subjected to a second spray drying treatment to obtain the second precursor;

[0062] Specifically, the equipment for the second spray drying process can include an open spray dryer or a closed spray dryer. The inlet temperature of the equipment can be 150℃-260℃, preferably 240℃, and the outlet temperature can be 60℃-150℃, preferably 120℃.

[0063] Step 180: The second precursor is placed in the second sintering equipment for a second sintering, and then pulverized to obtain nano-scale fluoride solid electrolyte material.

[0064] Specifically, the second sintering equipment can be any one of a box furnace, tube furnace, pusher furnace, roller kiln, or rotary furnace. The specific conditions for the second sintering are as follows: the atmosphere is an inert atmosphere, specifically one or both of nitrogen and argon; the temperature is increased to 700℃-1100℃ at a heating rate of 1℃ / min-20℃ / min, and held for 1 hour-12 hours; preferably, the temperature is increased to 900℃-1000℃ at a heating rate of 2℃ / min-5℃ / min, and held for 6 hours.

[0065] During the second sintering process, the fluorine source with a lower melting point preferentially melts into a liquid phase, filling the gaps between particles, which can reduce the porosity of the material and enhance its density.

[0066] The equipment for pulverization can be a fluidized bed jet mill or a flat jet mill, with compressed air pressure of 2MPa-5MPa, preferably 3.5MPa-4MPa, and the dew point of the compressed air less than -20℃, preferably -30℃. Because the raw materials are all nano-sized particles reacting, they are easier to break down during the pulverization process, avoiding the energy consumption in the process of breaking down micron-sized particles into nano-powder.

[0067] The method for preparing nanoscale fluoride solid electrolyte materials provided in this invention involves the following steps: During the first grinding process, the collision and shear force between the grinding media and the raw materials cause the chemical bonds on the surface of the raw material particles to break, generating unsaturated dangling bonds. This enhances the surface activity of the particles and triggers the interconnection of the dangling bonds generated during grinding, resulting in a uniformly mixed, pre-bonded nanoscale slurry. During the first spray drying process, the solvent in the first mixed slurry is rapidly evaporated, and the raw materials achieve a pre-assembled state between particles through the interconnected dangling bonds. Subsequently, the first sintering process promotes the reaction and bonding of the raw materials. Simultaneously, the nanoscale particles and surface dangling bonds increase the surface activity of the particles, significantly improving the particle reaction diffusion rate. This accelerates the sintering rate, reduces the temperature and time of the raw material reaction, and solves the problem of high energy consumption in high-temperature calcination. The pre-sintering precursor and the fluorine source have different particle sizes. The smaller particle size of the fluorine source allows for uniform distribution within the pre-sintering precursor. After the second spray drying, the fluorine source is evenly distributed across the surface and interstices of the pre-sintering precursor. During the second sintering process, the fluorine source, with its lower melting point, preferentially melts to form a liquid phase, filling the gaps between particles, thus reducing the material's porosity and increasing its density. Because the raw materials are all nano-sized particles reacting, they are easier to break during the pulverization process, avoiding the energy consumption associated with hard crushing from micrometer-sized particles to nano-powder.

[0068] The nanoscale fluoride solid electrolyte material provided by this invention can be applied to energy storage devices such as supercapacitors, lithium-ion batteries, and dye-sensitized batteries.

[0069] To better understand the technical solution provided by the present invention, the following uses several specific examples to illustrate the specific process of preparing nanoscale fluoride solid electrolyte materials using the method provided in the above embodiments of the present invention, as well as the electrochemical characteristics of the prepared nanoscale fluoride solid electrolyte materials.

[0070] Example 1

[0071] This invention provides a nanoscale fluoride solid electrolyte material.

[0072] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 The molar ratio of Nb₂O₆F to lithium carbonate, lanthanum trioxide, and niobium pentoxide was used. These were then added to deionized water and subjected to a first grinding process in a planetary mixer to obtain a first mixed slurry with a solid content of 40% and a Dv₁₀ of 453 nm. The grinding speed was 1500 rpm, the grinding time was 4 hours, and the grinding media consisted of zirconia beads with a diameter of 0.3 mm.

[0073] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 220℃, and the outlet temperature is 120℃.

[0074] The third step involves placing the first precursor in a box furnace and heating it to 500°C at a rate of 5°C / min, holding it at that temperature for 6 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0075] The fourth step involves feeding the pre-sintered precursor and deionized water into a planetary mixer for a second grinding process, resulting in a second mixed slurry with a solid content of 30% and a Dv50 of 872 nm. The grinding speed is 1500 rpm, the grinding time is 3 hours, and the grinding media are zirconia beads with a diameter of 0.3 mm.

[0076] The fifth step involves a third grinding process using a planetary mixer to obtain a lithium fluoride slurry with a solid content of 20% and a Dv50 of 325 nm. The grinding speed is 2000 rpm, the grinding time is 4 hours, and the grinding media are 0.1 mm diameter zirconium oxide beads. The molar ratio of lithium carbonate, lanthanum trioxide, niobium pentoxide, and lithium fluoride is 0.125:0.29:1:1.

[0077] Step 6: Add the second mixed slurry to a planetary mixer and mix with the lithium fluoride slurry for 1 hour to obtain the third mixed slurry.

[0078] Step 7: The third mixed slurry undergoes a second spray drying process in an open spray dryer to obtain the second precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0079] Step 8: The second precursor is placed in a rotary kiln, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 1000℃ at a rate of 5℃ / min, held for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Nb₂O₆F, wherein the pressure of the compressed air used for pulverization is 3.5 MPa and the dew point of the compressed air is -30℃.

[0080] Example 2

[0081] This invention provides a nanoscale fluoride solid electrolyte material.

[0082] The first step is to use the fluoride solid electrolyte Li 1.5 La 0.5The molar ratio of Nb₂O₆F was determined by lithium hydroxide, lanthanum trioxide, and niobium pentoxide, which were then added to deionized water and subjected to a first grinding process in a planetary mixer to obtain a first mixed slurry with a solid content of 30% and a Dv₁₀ of 417 nm. The grinding speed was 2000 rpm, the grinding time was 4 hours, and the grinding media were zirconia beads with a diameter of 0.3 mm.

[0083] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0084] The third step involves placing the first precursor in a box furnace and heating it to 600°C at a rate of 5°C / min, holding it at that temperature for 4 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0085] The fourth step involves feeding the pre-sintered precursor and deionized water into a planetary mixer for a second grinding process, resulting in a second mixed slurry with a solid content of 30% and a Dv50 of 725 nm. The grinding speed is 1500 rpm, the grinding time is 4 hours, and the grinding media consists of 0.3 mm diameter zirconia beads.

[0086] The fifth step involves a third grinding process using a planetary mixer to obtain a lithium fluoride slurry with a solid content of 20% and a Dv50 of 307 nm. The grinding speed is 2000 rpm, the grinding time is 4 hours, and the grinding media are 0.1 mm diameter zirconium oxide beads. The molar ratio of lithium hydroxide, lanthanum trioxide, niobium pentoxide, and lithium fluoride is 0.5:0.25:1:1.

[0087] Step 6: Add the second mixed slurry to a planetary mixer and mix with the lithium fluoride slurry for 1 hour to obtain the third mixed slurry.

[0088] Step 7: The third mixed slurry undergoes a second spray drying process in an open spray dryer to obtain the second precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0089] Step 8: The second precursor is placed in a rotary kiln, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 900℃ at a rate of 2℃ / min, held for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.5 La 0.5 Nb₂O₆F, wherein the pressure of the compressed air used for pulverization is 4.0 MPa and the dew point of the compressed air is -30℃.

[0090] Example 3

[0091] This invention provides a nanoscale fluoride solid electrolyte material.

[0092] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 Ti 0.5 NbW 0.5 The elemental molar ratio of O6F, consisting of lithium carbonate, lanthanum trioxide, titanium dioxide, niobium pentoxide, and tungsten oxide, was added to deionized water and subjected to a first grinding process in a planetary mixer to obtain a first mixed slurry with a solid content of 30% and a Dv100 of 474 nm. The grinding speed was 1500 rpm, the grinding time was 4 hours, and the grinding media consisted of 0.3 mm diameter zirconia beads.

[0093] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0094] The third step involves placing the first precursor in a box furnace and heating it to 600°C at a rate of 5°C / min, holding it at that temperature for 4 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0095] The fourth step involves feeding the pre-sintered precursor and deionized water into a planetary mixer for a second grinding process, resulting in a second mixed slurry with a solid content of 30% and a Dv50 of 725 nm. The grinding speed is 2000 rpm, the grinding time is 2.5 hours, and the grinding media are zirconia beads with a diameter of 0.3 mm.

[0096] The fifth step involves a third grinding process using a planetary mixer to obtain a lithium fluoride slurry with a solid content of 20% and a Dv50 of 323 nm. The grinding speed is 2000 rpm, the grinding time is 4 hours, and the grinding media consists of 0.1 mm diameter zirconium oxide beads. The molar ratio of lithium carbonate, lanthanum trioxide, titanium dioxide, niobium pentoxide, tungsten oxide, and lithium fluoride is 0.125:0.29:0.5:0.5:0.5:1.

[0097] Step 6: Add the second mixed slurry to a planetary mixer and mix with the lithium fluoride slurry for 1 hour to obtain the third mixed slurry.

[0098] Step 7: The third mixed slurry undergoes a second spray drying process in an open spray dryer to obtain the second precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0099] Step 8: The second precursor is placed in a rotary kiln, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 1000℃ at a rate of 2℃ / min, held for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Ti 0.5 NbW 0.5 O6F, wherein the pressure of the compressed air used for pulverization is 4.0 MPa and the dew point of the compressed air is -30℃.

[0100] Example 4

[0101] This invention provides a nanoscale fluoride solid electrolyte material.

[0102] The first step is to use the fluoride solid electrolyte Li 1.25 La 1.25 The elemental molar ratio of Ti2O6F was determined by lithium hydroxide, lanthanum trioxide, and titanium dioxide, which were then added to deionized water and subjected to a first grinding process in a planetary mixer to obtain a first mixed slurry with a solid content of 20% and a Dv100 of 479 nm. The grinding speed was 2000 rpm, the grinding time was 4 hours, and the grinding media were zirconia beads with a diameter of 0.3 mm.

[0103] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0104] The third step involves placing the first precursor in a box furnace and heating it to 500°C at a rate of 2°C / min, holding it at that temperature for 4 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0105] The fourth step involves feeding the pre-sintered precursor and deionized water into a planetary mixer for a second grinding process, resulting in a second mixed slurry with a solid content of 30% and a Dv50 of 764 nm. The grinding speed is 1500 rpm, the grinding time is 4 hours, and the grinding media are zirconia beads with a diameter of 0.3 mm.

[0106] The fifth step involves a third grinding process using a planetary mixer to obtain a lithium fluoride slurry with a solid content of 20% and a Dv50 of 293 nm. The grinding speed is 2000 rpm, the grinding time is 5 hours, and the grinding media are 0.1 mm diameter zirconium oxide beads. The molar ratio of lithium hydroxide, lanthanum trioxide, titanium dioxide, and lithium fluoride is 0.25:0.625:2:1.

[0107] Step 6: Add the second mixed slurry to a planetary mixer and mix with the lithium fluoride slurry for 1 hour to obtain the third mixed slurry.

[0108] Step 7: The third mixed slurry undergoes a second spray drying process in an open spray dryer to obtain the second precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0109] Step 8: The second precursor is placed in a rotary kiln, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 900℃ at a rate of 2℃ / min, held for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 1.25 Ti2O6F, wherein the pressure of the compressed air used for pulverization is 4.0 MPa and the dew point of the compressed air is -30℃.

[0110] Example 5

[0111] This invention provides a nanoscale fluoride solid electrolyte material.

[0112] The first step is to use the fluoride solid electrolyte Li 0.75 La 0.42 The elemental molar ratio of Sb1Mo1O6F was lithium oxalate, lanthanum carbonate, antimony pentoxide, and molybdenum trioxide. These were then fed with ethanol into a high-energy ball mill for the first grinding process, yielding a first mixed slurry with a solid content of 60% and a Dv100 of 453 nm. The grinding speed was 1000 rpm, the grinding time was 12 hours, and the grinding media consisted of glass beads with a diameter of 0.5 mm.

[0113] The second step involves performing a first spray drying treatment on the first mixed slurry in a closed-loop spray dryer to obtain the first precursor. The inlet temperature is 180℃, and the outlet temperature is 60℃.

[0114] The third step involves placing the first precursor in a box furnace and heating it to 200°C at a rate of 10°C / min, holding it at that temperature for 8 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0115] The fourth step involves feeding the pre-sintered precursor and ethanol into a high-energy ball mill for a second grinding process, yielding a second mixed slurry with a solid content of 30% and a Dv50 of 852 nm. The grinding speed is 1000 rpm, the grinding time is 12 hours, and the grinding media consists of glass beads with a diameter of 0.5 mm.

[0116] The fifth step involves a third grinding process using a high-energy ball mill to obtain an aluminum fluoride slurry with a solid content of 45% and a Dv50 of 225 nm. The grinding speed is 3000 rpm, the grinding time is 1 hour, and the grinding media consists of 0.5 mm diameter glass beads. The molar ratio of lithium oxalate, lanthanum carbonate, antimony pentoxide, molybdenum trioxide, and aluminum fluoride is 0.375:0.21:0.5:1:1.

[0117] Step 6: Add the second mixed slurry to a high-energy ball mill and mix it with the aluminum fluoride slurry for 1 hour to obtain the third mixed slurry.

[0118] Step 7: The third mixed slurry undergoes a second spray drying process in a closed-loop spray dryer to obtain the second precursor. The inlet temperature is 260℃, and the outlet temperature is 150℃.

[0119] Step 8: The second precursor is placed in a rotary furnace, and argon gas is introduced to maintain an argon atmosphere. The temperature is increased to 700℃ at a rate of 1℃ / min and held for 12 hours. Afterwards, it is pulverized using a flat-type airflow pulverizer to obtain nanoscale fluoride solid electrolyte material Li. 0.75 La 0.42 Sb1Mo1O6F, wherein the pressure of the compressed air used for pulverization is 5 MPa and the dew point of the compressed air is -30℃.

[0120] Example 6

[0121] This invention provides a nanoscale fluoride solid electrolyte material.

[0122] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 The elemental molar ratio of Ta2O6F was determined by lithium acetate, lanthanum nitrate, and tantalum pentoxide, which were then added to isopropanol in a vertical mixing tank for the first grinding process, resulting in a first mixed slurry with a solid content of 5% and a Dv100 of 353 nm. The grinding speed was 3000 rpm, the grinding time was 1 hour, and the grinding media were zirconium silicate beads with a diameter of 0.05 mm.

[0123] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 260℃, and the outlet temperature is 150℃.

[0124] The third step involves placing the first precursor in a tube furnace and heating it to 600°C at a rate of 1°C / min, holding it at that temperature for 1 hour, and then performing the first sintering to obtain the pre-sintered precursor.

[0125] The fourth step involves adding the pre-sintered precursor and isopropanol to a vertical mixing tank for a second grinding process, resulting in a second mixed slurry with a solid content of 30% and a Dv50 of 752 nm. The grinding speed is 3000 rpm, the grinding time is 1 hour, and the grinding media are zirconium silicate beads with a diameter of 0.05 mm.

[0126] Step 5: Ammonium fluoride and isopropanol are subjected to a third grinding process in a vertical mixing tank to obtain an ammonium fluoride slurry with a solid content of 1% and a Dv50 of 50 nm. The grinding speed is 1000 rpm, the grinding time is 12 hours, and the grinding media are 0.1 mm diameter zirconium silicate beads. The molar ratio of lithium acetate, lanthanum nitrate, tantalum pentoxide, and ammonium fluoride is 1.25:0.58:1:1. Step 6: The second mixed slurry is added to the vertical mixing tank and mixed with the ammonium fluoride slurry for 1 hour to obtain a third mixed slurry.

[0127] Step 7: The third mixed slurry undergoes a second spray drying process in an open spray dryer to obtain the second precursor. The inlet temperature is 180℃, and the outlet temperature is 60℃.

[0128] Step 8: The second precursor is placed in a roller mill, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 1100℃ at a rate of 10℃ / min, held for 1 hour, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Ta2O6F, wherein the pressure of the compressed air used for pulverization is 2MPa and the dew point of the compressed air is -40℃.

[0129] Comparative Example 1

[0130] This comparative example prepares a conventional fluoride solid electrolyte material.

[0131] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 The first mixture of Nb2O6F is obtained by mixing lithium carbonate, lanthanum trioxide, and niobium pentoxide in the same molar ratio.

[0132] The second step involves placing the first mixture in a box furnace and heating it to 500°C at a rate of 5°C / min, holding it at that temperature for 6 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0133] The third step is to mix the pre-sintered precursor and lithium fluoride according to Li... 1.25 La 0.58After Nb₂O₆F was mixed in a specific molar ratio, it was placed in a box furnace and heated to 1000℃ at a rate of 5℃ / min under a nitrogen atmosphere, held at that temperature for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Nb₂O₆F, wherein the pressure of the compressed air used for pulverization is 3.5 MPa, and the dew point of the compressed air is -30℃. The molar ratio of lithium carbonate, lanthanum trioxide, niobium pentoxide, and lithium fluoride is 0.125:0.29:1:1.

[0134] Comparative Example 2

[0135] This comparative example prepares a conventional fluoride solid electrolyte material.

[0136] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 The molar ratio of Nb₂O₆F to lithium carbonate, lanthanum trioxide, and niobium pentoxide was used. These were then added to deionized water and subjected to a first grinding process in a planetary mixer to obtain a first mixed slurry with a solid content of 40% and a Dv₁₀ of 471 nm. The grinding speed was 1500 rpm, the grinding time was 4 hours, and the grinding media consisted of zirconia beads with a diameter of 0.3 mm.

[0137] The second step involves performing a first spray drying treatment on the first mixed slurry in an open spray dryer to obtain the first precursor. The inlet temperature is 220℃, and the outlet temperature is 120℃.

[0138] The third step involves placing the first precursor in a box furnace and heating it to 500°C at a rate of 5°C / min, holding it at that temperature for 6 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0139] The fourth step involves mixing the pre-sintered precursor with lithium fluoride according to the Li... 1.25 La 0.58 The molar ratio of Nb₂O₆F was mixed and placed in a box furnace, heated to 1000℃ at a rate of 5℃ / min under a nitrogen atmosphere, and held at that temperature for 6 hours. Afterwards, it was pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Nb₂O₆F, wherein the pressure of the compressed air used for pulverization is 3.5 MPa, and the dew point of the compressed air is -30℃. The molar ratio of lithium carbonate, lanthanum trioxide, niobium pentoxide, and lithium fluoride is 0.125:0.29:1:1.

[0140] Comparative Example 3

[0141] This comparative example prepares a conventional fluoride solid electrolyte material.

[0142] The first step is to use the fluoride solid electrolyte Li 1.25 La 0.58 The elemental molar ratio of Nb2O6F is obtained by first mixing lithium carbonate, lanthanum trioxide, and niobium pentoxide to obtain the first mixture.

[0143] The second step involves placing the first mixture in a box furnace and heating it to 500°C at a rate of 5°C / min, holding it at that temperature for 6 hours, and then performing the first sintering to obtain the pre-sintered precursor.

[0144] The third step involves grinding lithium fluoride and deionized water in a planetary mixer to obtain a lithium fluoride slurry with a solid content of 20% and a Dv50 of 337 nm. The grinding speed is 2000 rpm, the grinding time is 4 hours, and the grinding media are 0.1 mm diameter zirconium oxide beads. The molar ratio of lithium carbonate, lanthanum trioxide, niobium pentoxide, and lithium fluoride is 0.125:0.29:1:1.

[0145] The fourth step is to put the pre-sintered precursor into a planetary mixer and mix it with the lithium fluoride slurry for 1 hour to obtain a mixed slurry.

[0146] The fifth step involves spray drying the mixed slurry in an open spray dryer to obtain the precursor. The inlet temperature is 240℃, and the outlet temperature is 120℃.

[0147] Step 6: The precursor is placed in a rotary kiln, nitrogen gas is introduced to maintain a nitrogen atmosphere, and the temperature is increased to 1000℃ at a rate of 5℃ / min, held for 6 hours, and then pulverized using a fluidized bed jet mill to obtain nanoscale fluoride solid electrolyte material Li. 1.25 La 0.58 Nb₂O₆F, wherein the pressure of the compressed air used for pulverization is 3.5 MPa and the dew point of the compressed air is -30℃.

[0148] The test methods for various parameters of the electrolytes prepared in Examples 1-4 and Comparative Examples 1-3 are as follows:

[0149] Test Method 1: The density test is conducted using the following method:

[0150] 1. Sample preparation: The nano-sized fluoride solid electrolyte was pressed into ceramic sheets using a tablet press, and then sintered at 1000℃ for 5 hours to densify it, resulting in a densified ceramic sheet sample. The obtained ceramic sheet sample was then placed in a drying oven at 110℃ for 2 hours.

[0151] 2. Use an analytical balance to measure the mass W of nanoscale fluoride solid electrolyte in air. (空气) 3. Place the ceramic sample on the sample holder, connect the sample holder to an analytical balance to test the sample mass, and place the sample holder in deionized water to obtain the mass W of the nano-sized fluoride solid electrolyte in deionized water under the action of buoyancy. (水) ;

[0152] According to the formula:

[0153] ρ=ρ (水) ×W (空气) / (W (空气) -W (水) )

[0154] α = (ρ / ρ0) * 100%

[0155] ρ is the bulk density of the nano-sized fluorine compound solid electrolyte ceramic sheet, expressed in grams per cubic centimeter (g / cm³). 3 );

[0156] W (空气) The mass of the nano-sized fluorine compound solid electrolyte ceramic sheet in air is expressed in grams (g).

[0157] W (水) The mass of the nano-sized fluorine compound solid electrolyte ceramic sheet in deionized water is expressed in grams (g).

[0158] ρ (水) This refers to the density of water, expressed in grams per cubic centimeter (g / cm³). 3 );

[0159] ρ0 is the theoretical density of the nano-sized fluorine compound solid electrolyte ceramic sheet, in grams per cubic centimeter (g / cm³). 3 )

[0160] Test Method 2: The particle size Dv50 of the material refers to the median particle size by volume, which is the median value sorted by volume. In the embodiments of this invention, the median particle size sorted by volume is specifically used, representing the particle size in the mixed slurry with a volume distribution of 50%. The particle size Dv100 refers to the maximum particle size by volume, which is the maximum value sorted by volume. In the embodiments of this invention, the maximum particle size sorted by volume is specifically used, representing the particle size in the mixed slurry with a cumulative volume distribution of 100%. Particle size Dv50 and particle size Dv100 are well-known in the art. The particle size Dv50 and particle size Dv100 of the materials provided in the embodiments of this invention can be determined by instruments and conventional methods known in the art. Specifically, in the embodiments of this invention, the Mastersizer 3000 laser particle size analyzer from Malvern Instruments Ltd., UK, is used to determine the particle size Dv50 and particle size Dv100.

[0161] The test results for each parameter are recorded in Table 1 below.

[0162]

[0163] Table 1

[0164] As shown in Table 1, the electrolytes of Examples 1-4 of the present invention have higher densities than those of Comparative Examples 1-3. This is because the raw materials were nano-sized during the grinding process of this application, and the nano-sized raw materials were then ground and mixed with lithium fluoride of different particle sizes in the subsequent process, so that the lithium fluoride was evenly distributed in the precursor, which can improve the density of the material.

[0165] according to Figure 2 It can be seen that the conventional fluoride solid electrolytes prepared in Comparative Examples 1-3 have impurity peaks (indicated by black triangles), while the nanoscale fluoride solid electrolytes of Examples 1-2 of this invention have better phase purity. This is because nanoparticles have a higher specific surface area, providing more active sites for solid-phase reactions; moreover, the grain boundary diffusion distance of nanoparticles is shorter, which is beneficial to Li + The migration and homogenization of the phases reduce the impurity peaks caused by unreacted regions; at the same time, nano-sizing can release the internal stress of micron-sized particles, reduce lattice distortion, and reduce shoulder peaks or broadened impurity peaks caused by defects.

[0166] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a nanoscale fluoride solid electrolyte material, characterized in that, The preparation method includes: A non-fluorine-containing source is taken according to the molar ratio of each element in the fluoride solid electrolyte material, and is put into the first grinding equipment with the first solvent for the first grinding process to obtain the first mixed slurry; the particle size Dv100 of the first mixed slurry is less than 1000nm; The first mixed slurry was subjected to a first spray drying treatment to obtain a first precursor. The first precursor is placed in the first sintering equipment for the first sintering to obtain a pre-sintered precursor. The pre-sintered precursor and the second solvent are subjected to a second grinding process in a second grinding equipment to obtain a second mixed slurry; the particle size Dv50 of the second mixed slurry is 10nm-1000nm; The fluorine source and the third solvent are subjected to a third grinding process in a third grinding device to obtain a fluorine-containing slurry; the particle size Dv50 of the fluorine-containing slurry is 10nm-1000nm. The second mixed slurry is fed into the third grinding equipment and mixed to obtain the third mixed slurry; The third mixed slurry is subjected to a second spray drying treatment to obtain the second precursor; The second precursor is placed in a second sintering device for a second sintering, and then pulverized to obtain the nano-scale fluoride solid electrolyte material; The lithium source of the fluoride solid electrolyte material is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate; the lanthanum source of the fluoride solid electrolyte material is one or more of lanthanum trioxide, lanthanum carbonate, lanthanum nitrate, lanthanum hydroxide, and lanthanum fluoride; the fluorine source of the fluoride solid electrolyte material is one or more of ammonium fluoride, lithium fluoride, lanthanum fluoride, and aluminum fluoride; the fluoride solid electrolyte material is a fluoride solid electrolyte LLMOF, wherein the general chemical formula of LLMOF is Li x La y M1 z M2 w M3 u O6F, M1 is a tetravalent cation, M2 is a pentavalent cation, M3 is a hexavalent cation, and 1 < x + 3y ≤ 5, 0 < x ≤ 2, 1 / 3 < y < 5 / 3, 0 ≤ z ≤ 2, 0 ≤ w ≤ 2, 0 ≤ u ≤ 2, z + w + u = 2; M1 is one or more of Zr, Ti, Hf, Si, Ge, Sn, M2 is one or more of Nb, Sb, Bi, V, Ta, and M3 is one or more of W, Cr, Mo, Mn; The specific conditions for the first sintering are: heating to 200℃-600℃ at a heating rate of 1℃ / min-20℃ / min, and holding at that temperature for 1 hour-8 hours; The specific conditions for the second sintering are as follows: under an inert atmosphere, the temperature is increased to 700℃-1100℃ at a heating rate of 1℃ / min-10℃ / min, and held for 1 hour-12 hours. The inert atmosphere includes one or more combinations of nitrogen and argon.

2. The preparation method according to claim 1, characterized in that, The first solvent is one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone. The first grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, and a high-energy ball mill; the grinding media for the first grinding treatment is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm, and the grinding time is 1 hour-24 hours; The solid content of the first mixed slurry is 5%-60%; The equipment for the first spray drying process includes an open spray dryer or a closed spray dryer; the inlet temperature of the equipment is 150℃-260℃, and the outlet temperature is 60℃-150℃.

3. The preparation method according to claim 1, characterized in that, The first sintering equipment is any one of a box furnace, tube furnace, pusher furnace, roller kiln, or rotary furnace.

4. The preparation method according to claim 1, characterized in that, The second solvent is one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone. The second grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, or a high-energy ball mill; The grinding media for the second grinding process is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm; and the grinding time is 1 hour-24 hours.

5. The preparation method according to claim 1, characterized in that, The third solvent is one or more of deionized water, ethanol, N-methylpyrrolidone (NMP), isopropanol, and acetone. The third grinding equipment is any one of a horizontal sand mill, a vertical sand mill, a planetary mixer, a vertical mixing tank, or a high-energy ball mill. The grinding media for the third grinding process is one or more of glass beads, steel beads, zirconium silicate beads, and zirconium oxide beads; the diameter of the grinding media is one or more of 0.03mm, 0.05mm, 0.1mm, 0.3mm, 0.5mm, 0.8mm, and 1mm; the grinding speed is 500rpm-3000rpm; and the grinding time is 1 hour-24 hours. The solid content of the fluorinated slurry is 1%-60%; the ratio of the particle size Dv50 of the fluorinated slurry to that of the second mixed slurry is [0.01-0.5]:

1.

6. The preparation method according to claim 1, characterized in that, The equipment for the second spray drying process includes an open spray dryer or a closed spray dryer; the inlet temperature of the equipment is 150℃-260℃, and the outlet temperature is 60℃-150℃. The second sintering equipment is any one of the following: box furnace, tube furnace, pusher furnace, roller kiln, and rotary furnace.

7. The preparation method according to claim 1, characterized in that, The equipment used for the pulverization process is a fluidized bed jet mill or a flat jet mill, and the pressure of the compressed air is between 2MPa and 5MPa, with the dew point of the compressed air being less than -20℃.

8. A nanoscale fluoride solid electrolyte material, characterized in that, The nanoscale fluoride solid electrolyte material is prepared by any of the preparation methods described in claims 1-7.

9. A battery, characterized in that, The battery comprises the nanoscale fluoride solid electrolyte material as described in claim 8.

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