Method of manufacturing solid electrolyte oxide for lithium battery

Abstract

To provide a method of manufacturing a solid electrolyte oxide for a lithium battery.SOLUTION: Polishing is performed by injecting a zirconium compound and a lanthanum compound into a first ball mill having ultrapure water and methanol and oil bath decompression condensation is then performed. Next, a first stage sintering operation is performed to generate a nitrogen argon atmosphere sintering reaction to generate a zirconium lanthanum compound. Then, polishing is performed by injecting a lithium compound, a gallium compound, an aluminum compound, another lanthanum compound, and the zirconium lanthanum compound into a second ball mill containing ultrapure water, and oil bath decompression condensation is then performed. Next, a second stage sintering operation is performed to generate an aerobic sintering reaction to generate a plurality of modified LLZO blocks. Polishing is performed by injecting the plurality of modified LLZO blocks into a jet mill and a wet polisher, and water bath decompression condensation is then performed, to obtain modified LLZO powder, that is, a solid electrolyte oxide for a lithium battery.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a solid electrolyte, and more particularly to a method for producing a solid electrolyte oxide for a lithium battery. [Background technology]

[0002] The conventional method for manufacturing solid electrolytes for lithium batteries involves forming a mixed slurry from three initial compounds: zirconium dioxide (ZrO2), lanthanum oxide (La2O3), and lithium carbonate (Li2CO3), then putting the mixture into a ball mill for mixing and polishing, and then performing a one-time sintering process using oxygen. Summary of the Invention [Problem to be solved by the invention]

[0003] However, with this method, the heat exchange and phase inversion conditions between powder blocks are not consistent during the sintering process, causing partial oxides to lack oxygen or energy, preventing the correct phase (cubic phase). This leads to disorder during the phase transition process and reduced lithium ion conductivity in the final product. Although various preparation methods have been developed to address this issue, it is still difficult to unify the complex crystalline phases, accelerating lithium loss and degrading the octahedral crystalline LLZO (lithium lanthanum zirconium oxide), which has a stable phase. Even with lithium replenishment, the process becomes lengthy, resulting in excessive material and energy loss, inconvenient production and product control, and making the product difficult to commercialize.

[0004] Therefore, the present inventors believed that the above drawbacks could be improved, and as a result of extensive research, they came up with the proposal of the present invention, which effectively improves the above problems through rational design.

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to solve the above problems. That is, an object of the present invention is to provide a method for producing a solid electrolyte oxide for a lithium battery. [Means for solving the problem]

[0006] To address the above-mentioned problems, one embodiment of the present invention provides a method for producing a solid electrolyte oxide for lithium batteries. In the first sintering step, only nitrogen and argon are used to create an atmospheric smoldering protection and obtain a stable zirconium-lanthanum compound (LaZrO). In the second sintering step, lithium compounds and oxygen are added to uniformly stabilize the phase state of the intermediate product, resulting in stable modified LLZO particles with a cubic crystal lattice. This prevents lithium loss due to complex and lengthy sintering and prevents the deterioration and disruption of the phase state due to changes in the equivalent weight during sintering, thereby improving process yield and cost control. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a flowchart illustrating a manufacturing method according to an embodiment of the present invention. [Figure 2] 1 illustrates a schematic diagram of an example of a mixed slurry process according to an embodiment of the present invention. [Figure 3] 10A and 10B illustrate an example of processing the first mixed particles according to an embodiment of the present invention. [Figure 4] 10A and 10B illustrate a schematic example of processing the second mixed particles according to an embodiment of the present invention. [Figure 5] 10A and 10B are schematic diagrams illustrating an example of a grill groove according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0008] The following describes in detail the embodiments of the present invention, but the present invention is not limited to these, and various modifications are possible within the scope of the description, and embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0009] Next, one example of a specific embodiment of the method for producing a solid electrolyte oxide for a lithium battery of the present invention will be described in detail with reference to FIGS.

[0010] 1 is a flowchart showing a manufacturing method according to one embodiment of the present invention. The manufacturing method of a solid electrolyte oxide for a lithium battery according to the present invention mainly comprises the following steps:

[0011] As shown in FIG. 2, a first ball mill 100 is prepared, and ultrapure water and methanol are poured into the first ball mill 100 (step 500).

[0012] A solid material formed of a zirconium compound and a lanthanum compound is poured into the first ball mill 100, which then mixes it with the original ultrapure water and methanol in a specific weight ratio to form a mixed slurry 10. The first ball mill 100 mixes and polishes the mixed slurry 10 using a plurality of first zirconium beads 101 to reduce the particle size of the mixed slurry 10 to less than 500 nm, forming a plurality of first mixed particles 15 (step 510). The rotation speed of the first ball mill 100 is 2600 rpm ±20%, the particle size of the first zirconium beads 101 ranges from 0.8 mm to 1.2 mm, and the filling rate of the total volume of the mixed slurry 10 and the plurality of first zirconium beads 101 ranges from 65% to 80%, which is the ratio of the total volume of the mixed slurry 10 and the plurality of first zirconium beads 101 to the polishing volume of the first ball mill 100. The polishing time of the first ball mill 100 is 0.25 to 3 hours (preferably 0.25 to 1.5 hours). Regarding the mixing and polishing method of the first ball mill 100, the mixed slurry 10 is first poured into a first tank A, stirred, and then fed into the first ball mill 100 for polishing. Then, the mixed slurry 10 is fed into a second tank B, stirred, and then fed into the first ball mill 100 for polishing. The mixed slurry 10 is then fed into the first tank A, and the above process is repeated to repeatedly stir and polish the mixed slurry 10 until it is completely polished. The operating temperature of the first ball mill 100 is between 15°C and 30°C, preferably between 15°C and 25°C. The solid content of the mixed slurry 10 is between 25wt% and 40wt%.

[0013] The zirconium compound is selected from the group consisting of zirconium nitrate (Zr(NO3)4), zirconium dioxide (ZrO2), and zirconium hydroxide (Zr(OH)4). The lanthanum compound is selected from the group consisting of lanthanum nitrate (La(NO3)3), lanthanum oxide (La2O3), and lanthanum hydroxide (La(OH)3).

[0014] As shown in FIG. 2, subsequently, the first mixed particles 15 are subjected to oil bath vacuum concentration using an oil bath type vacuum concentration apparatus 200 to remove the ultrapure water and the methanol (step 520).

[0015] The oil bath temperature of the oil bath type vacuum concentrator 200 is 120°C, and the temperature of the condensed water in the oil bath type vacuum concentrator 200 is in the range of 0°C to 4°C, which completely evaporates the ultrapure water and the methanol from each of the first mixed particles 15, forming a plurality of microcavities on the surface of each of the first mixed particles 15. These microcavities increase the specific surface area of ​​each of the first mixed particles 15, which helps to adjust the sintering in the subsequent step and further improves the reaction speed and completeness.

[0016] Next, a first-stage sintering operation is performed to carry out a nitrogen-argon atmosphere sintering reaction. As shown in FIG. 3, the method involves first injecting the first mixed particles 15 obtained in step 520 into a sintering furnace and sintering them in a smoldering environment of a nitrogen and argon atmosphere to produce a zirconium-lanthanum compound (step 530). The volume ratio of nitrogen to argon is 98:2, and the temperature is increased to a range of 500°C to 700°C at a rate of 1°C to 5°C (preferably 2°C) per minute. The first mixed particles 15 are heated under the smoldering protection of the atmosphere for 3 to 9 hours (preferably 6 hours). The atmosphere is replaced and replenished at a rate of 0.05 L to 0.15 L per minute.

[0017] At this time, the plurality of first mixed particles 15 cause the nitrogen-argon atmosphere sintering reaction. The nitrogen-argon atmosphere sintering reaction is an oxygen-free sintering reaction, that is, the zirconium compound and the lanthanum compound in the plurality of first mixed particles 15 cause a reaction. In the first-stage sintering operation, the zirconium-lanthanum compound is produced as represented by the following general formula (1): JPEG2025177554000002.jpg8100

[0018] In the general formula (1), the molar ratio of ZrO2 to La2O3 is 2:1, and the chemical formula of the zirconium-lanthanum compound is La2Zr2O7. If the molar ratio is not within the above range, no reaction will occur; however, the initial compounds that do not react will remain in the final product. Therefore, the scope of the present invention includes mixtures of the initial compounds in various ratios. In the general formula (1), ZrO2 and La2O3 are the zirconium compound and the lanthanum compound, respectively, but this is not intended to limit the scope of the present invention.

[0019] 3, the zirconium-lanthanum compound (LaZrO) is poured into a second ball mill 110 containing ultrapure water, and a lithium compound (e.g., LiCO), a gallium compound (e.g., GaO), an aluminum compound (e.g., AlO), and another lanthanum compound (LaO) are added and mixed with the zirconium-lanthanum compound (LaZrO) and the ultrapure water to form a mixed material. The second ball mill 110 mixes and grinds the mixed material with a plurality of second zirconium beads 111 to reduce the particle size of the mixed material to less than 1000 nm, forming a plurality of small-sized second mixed particles 20 (step 540). The rotation speed of the second ball mill 110 is 3000 rpm ±20%, the particle size of the second zirconium beads 111 is in the range of 0.5 mm to 0.8 mm, and the filling rate of the total volume of the mixed material and the plurality of second zirconium beads 111 is in the range of 65% to 80%. This is the ratio of the total volume of the mixed material and the plurality of second zirconium beads 111 to the polishing volume of the second ball mill 110. The polishing time of the second ball mill 110 is in the range of 0.5 to 2 hours (preferably 0.5 to 1.5 hours). The mixing and polishing method of the second ball mill 110 is that the zirconium-lanthanum compound is first poured into a third tank C and stirred, and then introduced into the second ball mill 110 for polishing. The mixture is then fed into the fourth tank D for agitation, then into the second ball mill 110 for grinding, and then into the third tank C for repeated agitation and grinding, thus repeating the above process until the zirconium-lanthanum compound is completely ground. The operating temperature of the second ball mill 110 is in the range of 15°C to 30°C (preferably 15°C to 25°C).

[0020] Next, the plurality of second mixed particles 20 are subjected to oil bath vacuum concentration using the oil bath vacuum concentration apparatus 200 to remove the ultrapure water from the plurality of second mixed particles 20 (step 550). The oil bath temperature of the oil bath vacuum concentration apparatus 200 is 120°C, and the temperature of the condensed water from the oil bath vacuum concentration apparatus 200 is between 0°C and 4°C. The ultrapure water from the plurality of second mixed particles 20 is completely evaporated to form a plurality of small mixed particle blocks 22, i.e., sintered powder. A plurality of microcavities are formed on the surface of each mixed particle block 22, which increases the specific surface area of ​​each mixed particle block 22 and helps regulate the sintering in the subsequent step, further improving the reaction speed and completeness.

[0021] The lithium compound is selected from the group consisting of lithium nitrate (LiNO3), lithium carbonate (Li2CO3), and lithium hydroxide (LiOH). The gallium compound is selected from the group consisting of gallium nitrate (Ga(NO3)3), gallium oxide (Ga2O3), and gallium hydroxide (Ga(OH)3). The aluminum compound is selected from the group consisting of aluminum oxide (Al2O3), aluminum hydroxide (Al(OH)3), and aluminum nitrate (Al(NO3)3).

[0022] In the process of the present invention, zirconium dioxide (ZrO2), lanthanum oxide (La2O3), lithium carbonate (Li2CO3), gallium oxide (Ga2O3), and aluminum oxide (Al2O3) are used as the zirconium compound, the lanthanum compound, the lithium compound, the gallium compound, and the aluminum compound, respectively, but the present invention is not limited thereto. The process described below also applies to all combinations of compounds allowed in the five sources of the zirconium compound, the lanthanum compound, the lithium compound, the gallium compound, and the aluminum compound described above.

[0023] Next, a second-stage sintering operation is performed to generate an oxygen-assisted sintering reaction, in which the temperature of the mixed particle blocks 22 is raised to 780°C to 950°C, and then the mixed particle blocks 22 are heated and sintered at this temperature for 4 to 12 hours (preferably more than 6 hours) in an "oxygen-enriched environment." During this sintering, the lithium compound, the gallium compound, the aluminum compound, and the additional lanthanum compound in the mixed particle blocks 22 undergo an oxygen-assisted sintering reaction with oxygen (O) and the zirconium-lanthanum compound (LaZrO), generating a plurality of modified lithium lanthanum zirconium oxide (LLZO) particles (step 560). In this example, four compounds, lithium carbonate (Li2CO3), gallium oxide (Ga2O3), aluminum oxide (Al2O3), and lanthanum oxide (La2O3), and oxygen (O2) are involved in the aerobic sintering reaction with the zirconium-lanthanum compound (La2Zr2O7).

[0024] The second sintering step is carried out by increasing the temperature at a rate of 1 to 3°C per minute (preferably 2 to 4°C), adding 1 to 3 liters of oxygen per minute for every 200 g of sintered powder, and heating the mixture to 780 to 950°C for 4 to 12 hours (preferably more than 6 hours). During this process, the mixed particle blocks 22 formed after the first sintering step, which is subjected to the nitrogen-argon atmosphere sintering reaction and the grinding in the second ball mill 110, undergo the reaction of formula (2), producing the modified LLZO particles composed of cubic crystal lattices. The modified LLZO is Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 It is used as a solid electrolyte in lithium batteries to conduct lithium ions. Conventional LLZO (Li7La3Zr2O) produced without adding Ga and Al by conventional technology 12 ), the Li (7-x-y) Gax / 3 Al y / 3 La3Zr2O 12 Since gallium (Ga) and aluminum (Al) are added, the equivalence ratio (ER) of the lithium ion is reduced from 7 to 6.9 to 6.2. (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 The cubic crystalline structure of has large channels, which improves the conduction rate of lithium ions.

[0025] In the prior art, conventional LLZO (Li7La3Zr2O 12 When a lithium ion channel is used as a solid electrolyte between the positive and negative electrodes of a battery, the lithium ion channel has a limited conductivity for the lithium ions. Although it has a certain effect, it is not comparable to that of a liquid electrolyte, and therefore the lithium ion conduction rate is limited, which means that the charging and operation speeds are limited.

[0026] Therefore, the improved method of the present invention involves adding gallium oxide (Ga2O3) and aluminum oxide (Al2O3) separately to the conventional chemical reaction "La2Zr2O7+ Li2CO3+ O2" to convert the conventional LLZO (Li7La3Zr2O 12 ) to replace part of the lithium (Li) in (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 This is LLZO doped with gallium (Ga) and aluminum (Al). That is, the modified LLZO obtained by the present invention. (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 is a lithium-lanthanum-zirconium-gallium-aluminum compound, and the five initial compounds, i.e., the zirconium compound, the lanthanum compound, the lithium compound, the gallium compound, and the aluminum compound, are produced through the first and second sintering steps.

[0027] In the second-stage sintering operation, it is represented by the following general formula (2) for generating the modified LLZO. In the above general formula (2), x > 0, y > 0, and 7 - x - y > 0.

[0028] Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 In this case, Ga and Al replace a part of lithium (Li) in the conventional LLZO (Li7La3Zr2O 12 ). Since gallium (Ga) and aluminum (Al) have high charges and atomic sizes, Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 The crystal structure composed of the cubic crystal lattice of can generate a larger lithium ion channel, and it is possible to improve the conduction speed of lithium ions in the solid electrolyte.

[0029] A plurality of the modified LLZO particles are condensed as a plurality of modified LLZO blocks 40, and each of the modified LLZO blocks has a plurality of cubic crystal lattices.

[0030] In the general formula (2), the molar ratio of La2Zr2O7, Li2CO3, Ga2O3, Al2O3, and La2O3 is 2:(7 - x - y):x / 3:y / 3:1, and the reaction can occur without using this molar ratio. However, unreacted initial compounds remain in the final product. Therefore, the scope of the present invention includes combinations of the above initial compounds in various different ratios. In the general formula (2), 0 < x < 0.8, 0 < y < 0.8, and 0.1 < x + y < 0.8. Preferably, 0 < x < 0., 0 < y < 0.45, and 0.3 < x + y < 0.8.

[0031] In the present invention, a complete reaction is achieved when the first molar ratio of the zirconium compound and the lanthanum compound participating in the reaction in the first sintering operation and the second molar ratio of the lithium compound, the gallium compound, the aluminum compound, and the lanthanum compound participating in the reaction in the second sintering operation are the same as the corresponding molar ratios of the corresponding reaction coefficients in general formula (1) and general formula (2). If the first molar ratio or the second molar ratio differs from the corresponding molar ratio of the corresponding reaction coefficients in general formula (1) or general formula (2), a complete reaction is not achieved, and in this case, excess molecules of general formula (1) and general formula (2) form impurities. Such a procedure of producing impurities by preparing the mixture in a ratio incompatible with the complete reaction is also within the scope of the present invention.

[0032] Then, the modified LLZO blocks 40 are injected into a jet mill 300, and anhydrous ethanol solvent is injected into the jet mill 300 to mix with the modified LLZO blocks 40 to form a first mixed solvent having the modified LLZO blocks 40. The weight percentage of the modified LLZO blocks 40 in the first mixed solvent is in the range of 25 wt% to 45 wt%.

[0033] The jet mill 300 mixes and grinds the first mixed solvent with a plurality of third zirconium beads 301 to form a modified LLZO slurry 42 (step 570). The particle size of the modified LLZO slurry 42 is less than 500 nm. The rotation speed of the jet mill 300 is 3000 rpm ±20%, the particle size of the zirconium beads 301 is in the range of 0.3 mm to 1.2 mm, and the filling rate of the total volume of the first mixed solvent and the plurality of third zirconium beads 301 is in the range of 75% to 90%, which is the ratio of the total volume of the first mixed solvent and the plurality of third zirconium beads 301 to the grinding volume of the jet mill 300. The grinding time of the jet mill 300 is in the range of 1.5 to 8 hours (preferably 2 to 5 hours). The operating temperature of the jet mill 300 is in the range of 4°C to 30°C (preferably 8°C to 20°C).

[0034] Then, the modified LLZO slurry 42 is poured into a wet polisher 380 (step 580). Ethanol and water are poured into the wet polisher 380 and mixed with the modified LLZO slurry 42 to form a second mixed solvent containing the modified LLZO, and the weight percentage of the modified LLZO slurry 42 in the second mixed solvent is in the range of 25 wt% to 45 wt%.

[0035] The wet polisher 380 polishes the second mixed solvent with a plurality of fourth zirconium beads 381 to form a plurality of modified LLZO blockettes 46. The rotation speed of the wet polisher 380 is 3200 rpm ±15%, the particle size of each of the fourth zirconium beads 381 is in the range of 0.3 mm to 0.5 mm, and the filling rate of the total volume of the second mixed solvent and the plurality of fourth zirconium beads 381 is in the range of 80% to 95%, which is the ratio of the total volume of the second mixed solvent and the plurality of fourth zirconium beads 381 to the polishing volume of the wet polisher 380. The polishing time of the wet polisher 380 is in the range of 2 to 8 hours (preferably 2 to 4 hours), and the operating temperature of the wet polisher 380 is in the range of 4°C to 30°C (preferably 8°C to 20°C).

[0036] Then, the LLZO blockettes 46 are placed in a water bath vacuum concentrator 350 and subjected to water bath vacuum concentration at 40°C to 60°C to remove the ethanol and water from the LLZO blockettes 46, thereby obtaining a fine modified LLZO powder 44 composed of the modified LLZO. The temperature of the condensed water in the water bath vacuum concentrator 350 is in the range of 0°C to 4°C. When removing the ethanol and water, the LLZO blockettes 46 are subjected to dry concentration, the temperature is lowered to room temperature, and the ethanol and water from the LLZO blockettes 46 are evaporated (step 590).

[0037] In the present invention, nitrogen and argon are added to form the atmosphere in the first sintering step to prevent smoldering, thereby producing high-purity zirconium-lanthanum compound (La2Zr2O7). Once the reaction in the first sintering step is complete and a homogeneous intermediate is formed, oxygen is added in the second sintering step to induce the reaction of general formula (2). The resulting crystalline structure is primarily composed of cubic crystal lattices, which provides excellent lithium ion conductivity.

[0038] In order to accelerate the reaction rate, before the second-stage sintering operation, the mixed particle blocks 22 are first poured into a grill groove 50 (see FIG. 5). The grill groove 50 has a structure in which a storage groove is divided into a plurality of storage grids 54 by a plurality of isolation fences 52. Then, the mixed particle blocks 22 produced by the first ball mill 100 and the first-stage sintering operation are respectively poured into the storage grids 54, and the mixed particle blocks 22 are dispersed into many fine storage grids 54, thereby accelerating the reaction rate between the mixed particle blocks 22 and oxygen in the second-stage sintering operation.

[0039] The above description is for the purpose of explaining the present invention, and should not be construed as limiting the invention described in the claims or narrowing its scope. Furthermore, the configuration of each part of the present invention is not limited to the above embodiment, and various modifications are possible within the technical scope described in the claims. [Explanation of symbols]

[0040] 10 Mixed slurry 15 1st mixed particle 20 2nd mixed particles 22 Mixed Particle Blocks 40 Modified LLZO Block 42 Modified LLZO slurry 44 Modified LLZO powder 46 Modified LLZO blockette 50 Grill groove 52 Isolation Fence 54 Storage Lattice 100 First Ball Mill 101 First Zirconium Beads 110 No. 2 Ball Mill 111 Secondary Zirconium Beads 200 Oil bath type vacuum concentrator 300 Jet Mill 301 Third Zirconium Beads 350 Water bath type vacuum concentrator 380 Wet polishing machine 381 quaternary zirconium beads

Claims

1. Step A: preparing a first ball mill and injecting ultrapure water and methanol into the first ball mill; Step B: injecting a solid material containing a zirconium compound and a lanthanum compound into the first ball mill, mixing the solid material with ultrapure water and methanol in the first ball mill at a specific weight ratio to form a mixed slurry; and mixing and polishing the mixed slurry using a plurality of first zirconium beads in the first ball mill to reduce the particle size of the mixed slurry to a specific size or less to form a plurality of first mixed particles. a step C of subjecting the plurality of first mixed particles to oil bath vacuum concentration using an oil bath type vacuum concentration apparatus to evaporate the ultrapure water and methanol in the plurality of first mixed particles, thereby forming a plurality of microcavities on the surface of each of the first mixed particles; Step D: carrying out a first-stage sintering operation to generate a nitrogen-argon atmosphere sintering reaction, first injecting a plurality of the first mixed particles into a sintering furnace, and sintering in a smoldering environment having nitrogen and argon, and reacting the plurality of first mixed particles under the smoldering protection of the nitrogen and argon to produce a zirconium-lanthanum compound; Step E: pouring the zirconium-lanthanum compound into a second ball mill containing ultrapure water, and adding a lithium compound, a gallium compound, an aluminum compound, and another lanthanum compound, and mixing them with the zirconium-lanthanum compound and the ultrapure water to form a mixed material; and the second ball mill uses a plurality of second zirconium beads to mix and grind the mixed material, making the particle size of the mixed material less than 1000 nm, and forming a plurality of second mixed particles. Next, step F is to perform oil bath vacuum concentration on the plurality of second mixed particles using the oil bath type vacuum concentration apparatus, completely evaporating the ultrapure water in the plurality of second mixed particles, thereby generating a plurality of microcavities on the surfaces of the plurality of second mixed particles, and forming a plurality of mixed particle blocks, i.e., sintered powder; A second stage sintering operation is performed to generate an aerobic sintering reaction, and the plurality of mixed particle blocks are sintered, and at this time, the lithium compound, the gallium compound, the aluminum compound, and the additional lanthanum compound are sintered with oxygen (O 2 G. generating the aerobic sintering reaction between the gallium compound and the zirconium lanthanum compound to form a plurality of modified LLZO particles comprising modified lithium lanthanum zirconium oxide (LLZO); and condensing the plurality of modified LLZO particles into a plurality of modified LLZO blocks, each of the modified LLZO blocks comprising a plurality of cubic crystal lattices, wherein the gallium compound and the aluminum compound have a high charge and atomic size, thereby generating larger lithium ion channels throughout the crystalline structure comprising the plurality of modified LLZO particles and accelerating the conduction rate of lithium ions in the solid electrolyte; Then, the modified LLZO blocks are put into a jet mill, and anhydrous ethanol solvent is poured into the jet mill to be mixed with the modified LLZO blocks to form a first mixed solvent having the modified LLZO blocks, and the first mixed solvent is polished by the jet mill to form a modified LLZO slurry; Then, the modified LLZO slurry is put into a wet polishing machine, and ethanol and water are poured into the wet polishing machine to be mixed with the modified LLZO slurry to form a second mixed solvent containing the modified LLZO, and the second mixed solvent is polished by the wet polishing machine to form a plurality of modified LLZO blockets; Then, the modified LLZO blockets are poured into a water bath vacuum concentrator to be subjected to water bath vacuum concentration, and the ethanol and water in the modified LLZO blockets are evaporated to form a modified LLZO powder. The zirconium compound is zirconium nitrate (Zr(NO 3 ) 4 ), zirconium dioxide (ZrO 2 ), zirconium hydroxide (Zr(OH) 4 ), and the lanthanum compound is selected from lanthanum nitrate (La(NO 3 ) 3 ), lanthanum oxide (La 2 O 3 ), lanthanum hydroxide (La(OH) 3 ), and the lithium compound is selected from lithium nitrate (LiNO 3 ), lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), and the gallium compound is gallium nitrate Ga(NO 3 ) 3 , gallium oxide Ga 2 O 3 , gallium hydroxide Ga(OH) 3 and the aluminum compound is aluminum oxide Al 2 O 3 , aluminum hydroxide Al(OH) 3 , aluminum nitrate Al(NO 3 ) 3 10. A method for producing a solid electrolyte oxide for a lithium battery, comprising selecting one of the following:

2. The zirconium compound is zirconium dioxide (ZrO 2 ), and the lanthanum compound is lanthanum oxide (La 2 O 3 ), and the lithium compound is lithium carbonate (Li 2 CO 3 ), and the gallium compound is gallium oxide (Ga 2 O 3 ), and the aluminum compound is aluminum oxide (Al 2 O 3 ) and The zirconium-lanthanum compound produced in the first sintering step has the chemical formula La 2 Zr 2 O 7 and is represented by the following general formula (1) for producing the zirconium-lanthanum compound: Here, the modified LLZO produced in the second sintering operation is Li (7-x-y) Ga x / 3 Al y / 3 La 3 Zr 2 O 12 and is represented by the following general formula (2) for producing the modified LLZO:

2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein x>0, y>0, and 7-xy>0.

3. In the general formula (1), the molar ratio of ZrO 2 and La 2 O 3 is 2:

1. In the general formula (2), the molar ratios of the La 2 Zr 2 O 7 , Li 2 CO 3 , Ga 2 O 3 , Al 2 O 3 , La 2 O3 are 2:(7 - x - y):x / 3:y / 3:1, where 0 < x <

4. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step B, the weight percentage of the solid matter in the mixed slurry is in the range of 25 wt% to 40 wt%.

5. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step B, the particle size of the mixed slurry is less than 500 nm, the rotation speed of the first ball mill is 2600 rpm±20%, the particle size of each of the first zirconium beads is between 0.8 mm and 1.2 mm, the filling rate of the total volume of the mixed slurry and the plurality of first zirconium beads is between 65% and 80%, the polishing time of the first ball mill is between 0.25 and 3 hours, and the operation temperature is between 15°C and 30°C.

6. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step D, the volume ratio of nitrogen to argon is 98:

2.

7. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in the first-stage sintering operation of step D, the temperature is increased at a rate of 1°C to 5°C per minute to a temperature range of 500°C to 700°C, and the first mixed particles are heated for 3 to 9 hours under smoldering protection in an atmosphere formed by nitrogen and argon, and the atmosphere is replaced and replenished at a rate of 0.05 L to 0.15 L per minute.

8. 2. The method of claim 1, wherein in step E, the rotation speed of the second ball mill is 3000 rpm±20%, the particle size of each of the second zirconium beads is between 0.5 mm and 0.8 mm, the filling rate of the total volume of the mixed material and the plurality of second zirconium beads is between 65% and 80%, the grinding time of the second ball mill is between 0.5 and 2 hours, and the operation temperature is between 15°C and 30°C.

9. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in the second sintering operation of step G, the temperature of the mixed particle block is raised to a range between 780°C and 950°C, and then heated at this temperature for 4 to 12 hours in an "oxygen-enriched environment."

10. In step H, the weight percentage of the modified LLZO block in the first mixed solvent is between 25% and 45%, the jet mill mixes and grinds the first mixed solvent with a plurality of third zirconium beads to make the particle size of the first mixed solvent less than 500 nm, the rotation speed of the jet mill is 3000 rpm±20%, the particle size of the third zirconium beads is between 0.3 mm and 1.2 mm, the total volume filling rate of the first mixed solvent and the plurality of third zirconium beads is between 75% and 90%, the grinding time of the jet mill is between 1.5 and 8 hours, and the operating temperature is between 4°C and 30°C; 2. The method for manufacturing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step I, the weight percentage of the modified LLZO slurry in the second mixed solvent is between 25 wt% and 45 wt%, the wet polishing machine performs polishing using a plurality of fourth zirconium beads, the rotation speed of the wet polishing machine is 3200 rpm±15%, the particle size of the fourth zirconium beads is between 0.3 mm and 0.5 mm, the total volume filling rate of the second mixed solvent and the plurality of fourth zirconium beads is between 80% and 95%, the polishing time of the wet polishing machine is between 2 and 8 hours, and the operating temperature is between 4°C and 30°C.

11. In the second sintering step G, the temperature is increased at a rate of 1 to 3°C per minute, and 1 to 3 liters of oxygen is added per minute for every 200 g of the mixed particle block. The temperature is increased to 780 to 950°C, and the mixed particle blocks are heated at this temperature for 4 to 12 hours. During this time, the mixed particle blocks formed after the first sintering step and the grinding of the second ball mill react to produce the modified LLZO particles, which have a structure composed of a cubic crystal lattice. The modified LLZO particles are used as a solid electrolyte in a lithium battery to conduct lithium ions.

3. The method for producing a solid electrolyte oxide for a lithium battery according to claim 2, wherein a nitrogen-argon atmosphere sintering reaction in the first sintering step is used to produce the zirconium-lanthanum compound with high purity, and oxygen is added in the second sintering step to produce a plurality of the modified LLZO particles.

12. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein, before the second-stage sintering operation, the mixed particle blocks are first poured into a grill groove, which is a storage groove divided into a storage grid structure by a plurality of isolation fences, and then the mixed particle blocks are respectively poured into the storage grids, thereby accelerating the reaction rate between the mixed particle blocks and oxygen in the second-stage sintering operation.

13. 3. The method for producing a solid electrolyte oxide for a lithium battery according to claim 2, wherein when a first molar ratio of the zirconium compound and the lanthanum compound participating in the reaction in the first-stage sintering operation and a second molar ratio of the lithium compound, the gallium compound, the aluminum compound, and the lanthanum compound participating in the reaction in the second-stage sintering operation are the same as the corresponding molar ratios of the corresponding reaction coefficients of the general formula (1) and the general formula (2), a complete reaction is achieved; when the first molar ratio or the second molar ratio is different from the corresponding molar ratio of the corresponding reaction coefficients of the general formula (1) or the general formula (2), a complete reaction is not achieved, and in this case, excess molecules of the general formula (1) and the general formula (2) form impurities.

14. 2. The method for manufacturing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step B, the mixed slurry is first poured into a first tank and stirred, then fed into the first ball mill for polishing, then fed into a second tank and stirred, then fed into the first ball mill for polishing, and then fed into the first tank, where the mixed slurry is repeatedly stirred and polished, thereby completely polishing the mixed slurry.

15. 2. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, wherein in step C, the oil bath temperature of the oil bath type vacuum concentrator is 120°C, and the temperature of the condensed water of the oil bath type vacuum concentrator is in the range of 0°C to 4°C.

16. 2. The method of claim 1, wherein in step E, the zirconium-lanthanum compound is mixed and polished in the second ball mill by first pouring the zirconium-lanthanum compound into a third tank and stirring, then feeding the zirconium-lanthanum compound into the second ball mill for polishing, then feeding the zirconium-lanthanum compound into a fourth tank and stirring, then feeding the zirconium-lanthanum compound into the second ball mill for polishing, and then feeding the zirconium-lanthanum compound into the third tank.

3. The method of claim 1, wherein the zirconium-lanthanum compound is mixed and polished in the second ball mill by first pouring the zirconium-lanthanum compound into a third tank and stirring, then feeding the zirconium-lanthanum compound into the fourth tank and stirring, then feeding the zirconium-lanthanum compound into the second ball mill for polishing, and then feeding the zirconium-lanthanum compound into the third tank.

4. The method of claim 1, wherein the method of step E includes repeatedly pouring the zirconium-lanthanum compound into a third tank and stirring, then polishing the zirconium-lanthanum compound into the fourth tank and stirring, and then polishing the zirconium-lanthanum compound into the third tank.

5. The method of claim 1, wherein the method of step E includes repeatedly pouring the zirconium-lanthanum compound into a third tank and polishing the zirconium-lanthanum compound.

17. 2. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, wherein in step F, the oil bath temperature of the oil bath type vacuum concentrator is 120°C, and the temperature of the condensed water of the oil bath type vacuum concentrator is in the range of 0°C to 4°C.

Images