Method for manufacturing solid electrolyte oxides for lithium batteries

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 solid electrolytes, and more particularly to a method for producing solid electrolyte oxides for lithium batteries. [Background technology]

[0002] Conventional methods for manufacturing solid electrolytes for lithium batteries involve forming a mixed slurry from three initial compounds: zirconium dioxide (ZrO2), lanthanum oxide (La2O3), and lithium carbonate (Li2CO3). This slurry is then mixed and polished in a ball mill, followed by a single sintering process using oxygen. [Overview of the project] [Problems that the invention aims to solve]

[0003] However, in the above-mentioned method, the heat absorption and phase inversion conditions do not match between powder blocks during the sintering process, causing partial oxide depletion or energy deficiency, preventing the formation of the correct phase state (cubic phase). This leads to disorder during the phase transition process and a decrease in the lithium ion conduction efficiency of the final product. Although various adjustment methods have been developed to address this problem, unifying the complex crystalline phase remains difficult, accelerating lithium depletion and degrading the octahedral crystalline LLZO (lithium lanthanum zirconium oxide), which inherently possesses a stable phase. Even with lithium replenishment, the process becomes redundant, leading to excessive material and energy depletion, making production and product control inconvenient, and hindering the commercialization of the product.

[0004] Therefore, the inventors believed that the above-mentioned shortcomings could be improved, and after diligent research, arrived at the present invention, which effectively improves the above-mentioned problems through a rational design.

[0005] This invention has been made in view of the above circumstances, and one of its objectives is to solve the problems described above. That is, the object of this invention is to provide a method for producing a solid electrolyte oxide for lithium batteries. [Means for solving the problem]

[0006] To solve the above problems, a method for producing a solid electrolyte oxide for lithium batteries according to one aspect of the present invention involves forming atmospheric smoldering protection using only nitrogen and argon in a first-stage sintering operation to obtain a stable zirconium lanthanum compound (La2Zr2O7). In a second-stage sintering operation, lithium compound and oxygen are added to uniformly stabilize the phase state of the intermediate product, thereby producing stable modified LLZO particles having a cubic crystal lattice. In this way, the present invention prevents lithium depletion due to the complexity and redundancy of sintering, and also prevents deterioration and collapse of the phase state due to sintering caused by changes in the equivalent number, thereby improving process yield and cost control capabilities. [Brief explanation of the drawing]

[0007] [Figure 1] This flowchart shows a manufacturing method according to one embodiment of the present invention. [Figure 2] An example of a mixed slurry treatment according to one embodiment of the present invention is schematically shown. [Figure 3] An example of the processing of the first mixed particles according to one embodiment of the present invention is schematically shown. [Figure 4] An example of the processing of the second mixed particles according to one embodiment of the present invention is schematically shown. [Figure 5] An example of a grill groove according to one embodiment of the present invention is schematically shown. [Modes for carrying out the invention]

[0008] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and various modifications are possible within the described scope. Embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0009] Next, an example of a specific embodiment of the method for manufacturing a solid electrolyte oxide for a lithium battery according to the present invention will be described in detail with reference to FIGS. 1 to 5.

[0010] FIG. 1 is a flowchart showing a manufacturing method according to an embodiment of the present invention. The method for manufacturing 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 injected into the first ball mill 100 (step 500).

[0012] Inject the solid formed by the zirconium compound and the lanthanum compound into the first ball mill 100, and mix it with the original ultrapure water and methanol at a specific weight ratio to form a mixed slurry 10. The first ball mill 100 performs mixing and grinding with a plurality of first zirconium beads 101 to make the particle size of the mixed slurry 10 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 between 0.8 mm and 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 between 65% and 80%, which is the ratio of the total volume of the mixed slurry 10 and the plurality of first zirconium beads 101 to the grinding volume of the first ball mill 100. The grinding time of the first ball mill 100 is 0.25 to 3 hours (preferably 0.25 to 1.5 hours). The mixing and grinding method of the first ball mill 100 is to first inject the mixed slurry 10 into the first tank A for stirring, then let it enter the first ball mill 100 for grinding. Then, let it enter the second tank B for stirring and then enter the first ball mill 100 for grinding. Then, let it enter the first tank A, and repeat the above process so that stirring and grinding are repeated to completely grind all of the mixed slurry 10. The operating temperature of the first ball mill 100 ranges between 15°C and 30°C, and preferably, the operating temperature ranges between 15°C and 25°C. The ratio of the solid in the mixed slurry 10 ranges between 25 wt% and 40 wt%.

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

[0014] As shown in Figure 2, the oil bath vacuum concentration apparatus 200 is then used to perform oil bath vacuum concentration on the multiple first mixed particles 15 to remove the ultrapure water and 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, completely evaporating the ultrapure water and methanol from each of the first mixed particles 15 and creating multiple microcavities on each of the first mixed particles 15. These microcavities increase the specific surface area of ​​each of the first mixed particles 15, contributing to the adjustment of sintering in subsequent steps and further improving the reaction rate and integrity.

[0016] Next, a first-stage sintering operation is performed to carry out an argon and nitrogen atmosphere sintering reaction. As shown in Figure 3, the method involves first injecting the plurality of first mixed particles 15 obtained in step 520 into a sintering furnace and performing sintering 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 raised to a range of 500°C to 700°C at a heating rate of 1°C to 5°C per minute (preferably 2°C), and the plurality of first mixed particles 15 are heated for 3 to 9 hours (preferably 6 hours) under the smoldering protection of the atmosphere. The atmosphere is replaced and replenished at a rate of 0.05 L to 0.15 L per minute.

[0017] In this process, the plurality of first mixed particles 15 generate the nitrogen-argon atmosphere sintering reaction. The nitrogen-argon atmosphere sintering reaction is an oxygen-free sintering reaction, meaning that the zirconium compound and the lanthanum compound in the plurality of first mixed particles 15 react. The zirconium-lanthanum compound is produced in the first sintering operation by the following general formula (1). JPEG0007904871000001.jpg8100

[0018] In the general formula (1) above, the molar ratio of ZrO2 and La2O3 is 2:1, and the chemical formula of the zirconium lanthanum compound is La2Zr2O7. If the molar ratio is not as described above, the reaction will not occur, however, initial compounds that do not react will remain in the final product. Therefore, the scope of the present invention includes mixing of initial compounds in various different ratios. In the general formula (1) above, ZrO2 and La2O3 are represented as the zirconium compound and the lanthanum compound, respectively, but this is not to limit the scope of the present invention.

[0019] As shown in Figure 3, the zirconium lanthanum compound (La2Zr2O7) is injected into a second ball mill 110 containing ultrapure water, and a lithium compound (e.g., Li2CO3), a gallium compound (e.g., Ga2O3), an aluminum compound (e.g., Al2O3), and another lanthanum compound (La2O3) are added and mixed with the zirconium lanthanum compound (La2Zr2O7) and the ultrapure water to form a mixed material. The second ball mill 110 mixes and polishes 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 second mixed particles 20 (step 540). The rotational 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 multiple 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 multiple 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 to first inject the zirconium lanthanum compound into the third tank C and stir it, and then enter the second ball mill 110 for polishing. Then, the mixture is introduced into the fourth tank D and stirred, then into the second ball mill 110 for polishing, and finally into the third tank C, where the stirring and polishing are repeated, thereby repeating the above process to completely polish all of the zirconium lanthanum compound. 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] Then, the plurality of second mixed particles 20 described above are concentrated in an oil bath 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 in the oil bath vacuum concentration apparatus 200 is in the range of 0°C to 4°C, so that the ultrapure water in the plurality of second mixed particles 20 is completely evaporated and a plurality of small mixed particle blocks 22, i.e., sintered powder is formed. A plurality of microcavities are formed on the surface of each of the mixed particle blocks 22, and these microcavities increase the specific surface area of ​​each of the mixed particle blocks 22, which contributes to adjusting the sintering in the subsequent steps and further improves the reaction rate and integrity.

[0021] The lithium compound is selected from lithium nitrate (LiNO3), lithium carbonate (Li2CO3), and lithium hydroxide (LiOH). The gallium compound is selected from gallium nitrate (Ga(NO3)3), gallium oxide (Ga2O3), and gallium hydroxide (Ga(OH)3). The aluminum compound is selected from 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, lanthanum compound, lithium compound, gallium compound, and aluminum compound, respectively, but the present invention is not limited to these. The process described below also applies to all acceptable combinations of compounds in the five sources of the zirconium compound, lanthanum compound, lithium compound, gallium compound, and aluminum compound described above.

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

[0024] The operation method for the second stage sintering operation involves raising the temperature at a rate of 1°C to 3°C per minute (preferably 2°C to 4°C), adding 1 to 3 liters of oxygen per minute to every 200 g of the sintered powder, raising the temperature to 780 to 950°C, and heating at this temperature for 4 to 12 hours (preferably more than 6 hours). During this time, the reaction of general formula (2) is generated in the plurality of mixed particle blocks 22 formed after the nitrogen-argon atmosphere sintering reaction of the first stage sintering operation and the polishing of the second ball mill 110, thereby generating a plurality of 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 the addition of Ga and Al by conventional technology. 12 Compared to the Li according to the present invention (7-x-y) Gax / 3 Al y / 3 La3Zr2O 12 Since gallium (Ga) and aluminum (Al) are added, the equivalence ratio (ER) of its lithium ions decreases from 7 to 6.9 - 6.2. The above Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 has a large channel in its cubic crystal structure, so the conduction speed of lithium ions is improved.

[0025] In the prior art, when using conventional LLZO (Li7La3Zr2O 12 ) as the solid electrolyte between the positive and negative electrodes of the battery, there is a limit to the conduction effect on lithium ions generated by its lithium ion channels. Although there is a certain effect, it is not comparable to that of the liquid electrolyte, so the conduction speed of lithium ions is limited. That is, the charging and operating speeds are limited.

[0026] Therefore, the improvement method according to the present invention is to separately add gallium oxide (Ga2O3) and aluminum oxide (Al2O3) during the conventional chemical reaction "La2Zr2O7 + Li2CO3 + O2", and use gallium (Ga) and aluminum (Al) to replace a part of lithium (Li) in the conventional LLZO (Li7La3Zr2O 12 ) to form Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 which is used as LLZO doped with gallium (Ga) and aluminum (Al). That is, the modified LLZO obtained by the present invention. Li (7-x-y) Ga x / 3 Al y / 3 La3Zr2O 12 is a lithium - lanthanum - zirconium - gallium - aluminum compound, and the five initial compounds of the above zirconium compound, lanthanum compound, lithium compound, gallium compound, and aluminum compound are generated through the first - stage sintering operation and the second - stage sintering operation.

[0027] In the second-stage sintering operation, it is represented by the following general formula (2) for generating the modified LLZO. JPEG0007904871000002.jpg25165In 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 Among them, 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 rate 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 40 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. Although the reaction can occur without using this molar ratio, initial compounds that do not cause the reaction remain in the final product. Therefore, the scope of the present invention includes combinations of the above initial compounds with 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 < 0.35, 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 involved in the reaction in the first-stage sintering operation, and the second molar ratio of the lithium compound, the gallium compound, the aluminum compound, and the lanthanum compound involved in the reaction in the second-stage sintering operation, are both the same as the corresponding molar ratios of the corresponding reaction coefficients in general formula (1) and general formula (2). If the first or second molar ratio differs from the corresponding molar ratios of the corresponding reaction coefficients in general formula (1) or general formula (2), a complete reaction is not achieved, and in this case, the excess molecules of general formula (1) and general formula (2) form impurities. Operations that generate impurities by preparing compounds in ratios that do not conform to such a complete reaction are also included within the scope of the present invention.

[0032] Then, the multiple modified LLZO blocks 40 are injected into a jet mill 300, anhydrous ethanol solvent is injected into the jet mill 300 and mixed with the multiple modified LLZO blocks 40 to form a first mixed solvent containing the modified LLZO blocks. The weight percentage of the multiple 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 polishes 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 packing density 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 polishing volume of the jet mill 300. The polishing 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 injected into a wet polishing machine 380 (step 580). Ethanol and water are injected into the wet polishing machine 380 and mixed with the modified LLZO slurry 42 to form a second mixed solvent containing the modified LLZO, the weight percentage of the modified LLZO slurry 42 in the second mixed solvent being in the range of 25 wt% to 45 wt%.

[0035] The wet polishing machine 380 polishes the second mixed solvent with a plurality of fourth zirconium beads 381 to form a plurality of modified LLZO blocks 46. The rotational speed of the wet polishing machine 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 polishing machine 380. The polishing time of the wet polishing machine 380 is in the range of 2 to 8 hours (preferably 2 to 4 hours), and the operating temperature of the wet polishing machine 380 is in the range of 4°C to 30°C (preferably 8°C to 20°C).

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

[0037] In the present invention, nitrogen and argon are added during the first-stage sintering operation to form the atmosphere and provide protection against smoldering, thereby enabling the production of a high-purity zirconium lanthanum compound (La2Zr2O7). When the reaction in the first-stage sintering operation is completed and an intermediate with a uniform phase state is formed, oxygen is added only during the second-stage sintering operation to generate the reaction of general formula (2). The overall crystal structure formed in this situation is mainly composed of cubic crystal lattices, and its lithium ion conductivity is excellent.

[0038] To accelerate the reaction rate, before performing the second-stage sintering operation, a plurality of the mixed particle blocks 22 are first injected into the grill groove 50 (see Figure 5). The grill groove 50 has a structure in which the storage groove is divided into a plurality of storage grids 54 by a plurality of isolation fences 52. Then, the plurality of the mixed particle blocks 22 generated by the first ball mill 100 and the first-stage sintering operation are each placed into the storage grids 54, and the plurality of the mixed particle blocks 22 are dispersed into many minute storage grids 54, thereby accelerating the reaction rate between the plurality of 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 interpreted as limiting or restricting the scope of the invention described in the claims. Furthermore, it goes without saying that the configuration of each part of the present invention is not limited to the above embodiments and can be modified in various ways 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 block 40 Modified LLZO Block 42 Modified LLZO slurry 44 Modified LLZO powder 46 Modified LLZO Blockets 50 Grill grooves 52 Isolation fences 54 Storage Lattice 100 First Ball Mill 101 First Zirconium Bead 110 Second Ball Mill 111 Second Zirconium Bead 200 Oil bath type vacuum concentrator 300 Jet Mill 301 Third Zirconium Bead 350 Water bath type vacuum concentrator 380 Wet polishing machine 381. Fourth Zirconium Bead

Claims

1. Step A involves preparing a first ball mill and injecting ultrapure water and methanol into the first ball mill. Step B involves injecting a solid containing a zirconium compound and a lanthanum compound into the first ball mill, mixing it with ultrapure water and methanol in the first ball mill in a specific weight ratio to form a mixed slurry, the first ball mill mixing and polishing the mixed slurry with a plurality of first zirconium beads, and reducing the particle size of the mixed slurry to a specific size to form a plurality of first mixed particles. Step C involves performing oil bath vacuum concentration on a plurality of the first mixed particles using an oil bath type vacuum concentration apparatus, evaporating the ultrapure water and methanol in the plurality of first mixed particles, and forming a plurality of microcavities on the surface of each of the first mixed particles. Step D involves performing 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 performing sintering in an inert atmosphere containing nitrogen and argon, thereby reacting the plurality of the first mixed particles in the inert atmosphere to produce a zirconium lanthanum compound. Step E involves injecting the zirconium lanthanum compound into a second ball mill containing ultrapure water, 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, the second ball mill mixing and polishing the mixed material with a plurality of second zirconium beads to reduce the particle size of the mixed material to less than 1000 nm, and forming a plurality of second mixed particles. Next, step F is performed by concentrating the plurality of second mixed particles under reduced pressure in an oil bath using the oil bath type vacuum concentrator, completely evaporating the ultrapure water in the plurality of second mixed particles, generating a plurality of microcavities on the surface 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 multiple mixed particle blocks are sintered, during which the lithium compound, the gallium compound, the aluminum compound, and the other lanthanum compound are mixed with oxygen (O 2 Step G involves generating the aerobic sintering reaction with the gallium compound and the zirconium lanthanum compound to form a plurality of modified LLZO particles composed of modified lithium lanthanum zirconium oxide, condensing the plurality of modified LLZO particles into a plurality of modified LLZO blocks, each of which comprises a plurality of cubic crystal lattices, wherein the gallium compound and the aluminum compound have high charge and atomic size, generating even larger lithium ion channels throughout the crystal structure composed of the plurality of modified LLZO particles, and accelerating the conduction rate of lithium ions in the solid electrolyte. Then, step H involves placing a plurality of the modified LLZO blocks into a jet mill, injecting anhydrous ethanol solvent into the jet mill and mixing it with the plurality of modified LLZO blocks to form a first mixed solvent containing the plurality of modified LLZO blocks, and polishing the first mixed solvent with the jet mill to form a modified LLZO slurry. Step I involves then introducing the modified LLZO slurry into a wet polishing machine, injecting ethanol and water into the wet polishing machine and mixing them with the modified LLZO slurry to form a second mixed solvent containing the modified LLZO, and then polishing the second mixed solvent with the wet polishing machine to form a plurality of modified LLZO blocks. Then, step J includes injecting a plurality of the modified LLZO blocks into a water bath type vacuum concentration apparatus to perform water bath vacuum concentration, evaporating the ethanol and water in the plurality of modified LLZO blocks to form modified LLZO powder. The zirconium compound is selected from one of zirconium nitrate (Zr(NO 3 ) 4 ), zirconium dioxide (ZrO 2 ), and zirconium hydroxide (Zr(OH) 4 ). The lanthanum compound is selected from one of lanthanum nitrate (La(NO 3 ) 3 ), lanthanum oxide (La 2 O 3 ), and lanthanum hydroxide (La(OH) 3 ). The lithium compound is selected from one of lithium nitrate (LiNO 3 ), lithium carbonate (Li 2 CO 3 ), and lithium hydroxide (LiOH). The gallium compound is selected from one of gallium nitrate Ga(NO 3 ) 3 , gallium oxide Ga 2 O 3 , and gallium hydroxide Ga(OH) 3 . The aluminum compound is selected from one of aluminum oxide Al 2 Os 3 , aluminum hydroxide Al(OH) 3 , and aluminum nitrate Al(NO 3 ) 3 . A method for manufacturing a solid electrolyte oxide for a lithium battery, characterized in that one type is selected from the above.

2. The aforementioned 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 chemical formula of the zirconium lanthanum compound produced in the first sintering operation is La 2 Zr 2 O 7 The zirconium lanthanum compound is represented by the following general formula (1), 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 The above modified LLZO is represented by the following general formula (2), Herein, the method for producing a solid electrolyte oxide for a lithium battery according to claim 1 is characterized in that 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 ratio of the La 2 Zr 2 O 7 , Li 2 CO 3 , Ga 2 O 3 , Al 2 O 3 , La 2 O3 is 2:(7 - x - y):x / 3:y / 3:1, where 0 < x < 0.8, 0 < y < 0.8, and 0.1 < x + y < 0.

8. A method for producing a solid electrolyte oxide for a lithium battery according to claim 2, characterized by this.

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

5. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, 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 in the range of 0.8 mm to 1.2 mm, the packing density of the total volume of the mixed slurry and the plurality of first zirconium beads is in the range of 65% to 80%, the polishing time of the first ball mill is in the range of 0.25 to 3 hours, and the operating temperature is in the range of 15°C to 30°C.

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

2.

7. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, in the first sintering operation of step D, the temperature is raised at a heating rate of 1°C to 5°C per minute to a range of 500°C to 700°C, the first mixed particles are heated for 3 to 9 hours in an inert 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. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, in step E, the rotational speed of the second ball mill is 3000 rpm ± 20%, the particle size of each of the second zirconium beads is in the range of 0.5 mm to 0.8 mm, the filling rate of the total volume of the mixed material and the plurality of second zirconium beads is in the range of 65% to 80%, the polishing time of the second ball mill is in the range of 0.5 to 2 hours, and the operating temperature is in the range of 15°C to 30°C.

9. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, in the second sintering operation of step G, the temperature of the mixed particle block is raised to a range of 780°C to 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 in the range of 25% to 45%, the jet mill mixes and polishes the first mixed solvent with a plurality of third zirconium beads, the particle size of the first mixed solvent is reduced to less than 500 nm, the rotation speed of the jet mill is 3000 rpm ± 20%, the particle size of the third zirconium beads is in the range of 0.3 mm to 1.2 mm, the filling density of the total volume of the first mixed solvent and the plurality of third zirconium beads is in the range of 75% to 90%, the polishing time of the jet mill is in the range of 1.5 to 8 hours, and the operating temperature is in the range of 4°C to 30°C. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, in step I, the weight percentage of the modified LLZO slurry in the second mixed solvent is in the range of 25 wt% to 45 wt%, the wet polishing machine performs polishing with a plurality of fourth zirconium beads, the rotational speed of the wet polishing machine is 3200 rpm ± 15%, the particle size of the fourth zirconium beads is in the range of 0.3 mm to 0.5 mm, the filling rate of the total volume of the second mixed solvent and the plurality of fourth zirconium beads is in the range of 80% to 95%, the polishing time of the wet polishing machine is in the range of 2 to 8 hours, and the operating temperature is in the range of 4°C to 30°C.

11. In the second sintering operation of step G, the temperature is raised at a rate of 1°C to 3°C per minute, and 1 to 3 liters of oxygen per minute are added to each 200g block of mixed particles, raising the temperature to 780°C to 950°C. At this temperature, multiple blocks of mixed particles are heated for 4 to 12 hours. During this time, the multiple blocks of mixed particles formed after the first sintering operation and polishing in the second ball mill undergo a reaction, generating multiple modified LLZO particles, which have a structure composed of a cubic crystal lattice. These modified LLZO particles are used as a solid electrolyte in lithium batteries to conduct lithium ions. The method for producing a solid electrolyte oxide for lithium batteries according to claim 2, characterized in that the nitrogen-argon atmosphere sintering reaction in the first stage sintering operation is used to produce the zirconium lanthanum compound of high purity, and a plurality of modified LLZO particles are produced by adding oxygen in the second stage sintering operation.

12. The method for producing a solid electrolyte oxide for a lithium battery according to claim 1, characterized in that, before performing the second-stage sintering operation, a plurality of the mixed particle blocks are first injected into a grill groove, the grill groove being divided into a storage grid structure by a plurality of isolation fences, and then the plurality of the mixed particle blocks are placed into each of the storage grids, thereby accelerating the reaction rate between the plurality of mixed particle blocks and oxygen in the second-stage sintering operation.

13. The method for producing a solid electrolyte oxide for a lithium battery according to claim 2, characterized in that, in the first stage sintering operation, the first molar ratio of the zirconium compound and the lanthanum compound involved in the reaction, and in the second stage sintering operation, the second molar ratio of the lithium compound, the gallium compound, the aluminum compound, and the lanthanum compound involved in the reaction are both the same as the corresponding molar ratios of the corresponding reaction coefficients of general formula (1) and general formula (2), a complete reaction is achieved, and if the first molar ratio or the second molar ratio differs from the corresponding molar ratios of the corresponding reaction coefficients of general formula (1) or general formula (2), a complete reaction is not achieved, in which case the excess molecules of general formula (1) and general formula (2) form impurities.

14. In step B, the mixing and polishing method of the first ball mill is characterized in that the above process is repeated in a redundant manner, in which the mixing and polishing is performed, so as to be repeated to polish all of the mixed slurry.

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

16. In step E, the mixing and polishing method of the second ball mill is characterized in that the zirconium lanthanum compound is first injected into the third tank and stirred, then introduced into the second ball mill and polished, then introduced into the fourth tank and stirred, then introduced into the second ball mill and polished, then introduced into the third tank, and the above process is repeated in an overlapping manner so that the zirconium lanthanum compound is completely polished, as described in claim 1.

17. The method for producing a solid electrolyte oxide for lithium batteries according to claim 1, characterized in that, in step F, the oil bath temperature of the oil bath type vacuum concentrator is 120°C, and the temperature of the condensate in the oil bath type vacuum concentrator is in the range of 0°C to 4°C.

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