Method for manufacturing electrode application composite ceramic electrolyte particles coated with protective layer

Abstract

The invention discloses a method for manufacturing electrode application composite ceramic electrolyte particles coated with a protective layer. The method comprises the following steps: step A, preparing a plurality of LLZO particles; putting the methanol and the hydrophobic material into a wet mixer for mixing and grinding to form first mixed slurry; step B, adding trimethylolamine and trimethylolamine hydrochloric acid into the wet mixer for continuous stirring, and enabling OH-bonds of the trimethylolamine to extend towards the outer surfaces of the LLZO particles and the hydrophobic material so as to form a hydroxide ion layer; the rotating speed in the step B must be greater than that in the step A; c, adding dopamine hydrochloric acid into the wet mixer, and continuously grinding and stirring; wherein the OH-bond of dopamine in the dopamine hydrochloric acid and the OH-bond of the hydroxide ion layer are subjected to a dehydration polymerization reaction, a dopamine layer is formed due to aggregation among dopamine, and the hydrophobic material is coated on the LLZO particles with the dopamine layer to form the composite LLZO particles.

Description

Technical Field

[0001] This invention relates to the field of battery electrode materials technology, and in particular to a method for manufacturing composite ceramic electrolyte particles for electrode applications with a protective coating. Background Technology

[0002] A battery is mainly formed by placing a positive electrode and a negative electrode in an electrolyte. In conventional technology, LLZO material is added to the negative electrode to increase ionic conductivity. LLZO material has high ionic conductivity for lithium ions. Therefore, when lithium ions pass through the negative electrode, the dispersed LLZO particles guide the lithium ions, thus allowing for a uniform distribution of lithium ions within the negative electrode. This prevents abnormal accumulation of lithium ions in the negative electrode slurry and avoids side reactions with the slurry.

[0003] However, moisture is present during the manufacturing process of the negative electrode. Since LLZO material is hydrophilic, it is prone to react with water, causing it to become damp and generate alkaline substances, which leads to the deterioration of the material in the negative electrode slurry.

[0004] Therefore, existing technologies have shortcomings and need to be improved. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for manufacturing composite ceramic electrolyte particles for electrode application with a protective layer coating, so as to overcome the above-mentioned defects in the background technology.

[0006] The technical solution of this invention is as follows: A method for manufacturing composite ceramic electrolyte particles for electrode applications with a protective coating is provided. This method divides the traditional single-step mixing process into multiple mixing and grinding steps. Therefore, the entire reaction process is longer, and the LLZO particles are finer with a larger surface area. This allows the LLZO particles to react effectively and fully with tris(hydroxymethyl)amine and dopamine hydrochloride, thus forming a more robust external dopamine layer. Furthermore, multiple hydrophobic barium titanate particles or multiple hydrophobic zinc oxide particles are coated on the outer surface of the dopamine-coated LLZO particles, thus forming further hydrophobic protection. Therefore, the entire composite LLZO particle structure has enhanced lithium conductivity, and the reaction with water is avoided during electrode manufacturing, achieving better battery electrode material manufacturing quality.

[0007] To achieve the above objectives, this invention proposes a method for manufacturing composite ceramic electrolyte particles for electrode applications with a protective coating, wherein the composite ceramic electrolyte particles are multiple composite LLZO (lithium lanthanum zirconium oxide) particles; the process for manufacturing the composite ceramic electrolyte particles for electrode applications with a hydrophobic protective coating includes the following steps: Step A: Multiple LLZO particles, methanol, and a hydrophobic material are placed in a wet mixer for mixing and grinding to form a first mixed slurry, wherein the hydrophobic material is at least one of multiple barium titanate particles or multiple zinc oxide particles, or a mixture thereof; wherein multiple zirconium beads are placed in the wet mixer for mixing and grinding, so that the particle size of the multiple LLZO particles is less than 500 nanometers; Step B: Tris(hydroxymethyl)amine and trihydroxymethyl... Methylamine hydrochloric acid is added to the wet mixer and continues to grind and stir with the first mixed slurry to form a second mixed slurry. The tris(hydroxymethyl)amine itself has three OH- bonds, two of which form hydrogen bonds with the oxidized functional groups on the surface of the LLZO particles and the hydrophobic material; the third OH- bond of the tris(hydroxymethyl)amine extends towards the outer surface of the LLZO particles and the hydrophobic material, thus forming a hydroxyl ion layer on the outer surface of the LLZO particles and the hydrophobic material. In step B, after adding the tris(hydroxymethyl)amine and tris(hydroxymethyl)amine hydrochloric acid, the rotation speed of the wet mixer is increased; this rotation speed must be greater than the rotation speed in step A. Step C: Dopamine hydrochloric acid is added to the wet mixer and continues to grind and stir with the second mixed slurry from step B. The mixture is stirred to form a third slurry; wherein the OH- bonds of dopamine in the dopamine hydrochloride react with the OH- bonds of the hydroxide ion layer coating the LLZO particles and the hydrophobic material to undergo a dehydration polymerization reaction, allowing dopamine to combine with the LLZO particles and the hydrophobic material. Due to the copolymerization reaction between dopamine particles, a dopamine layer is formed, which collectively forms multiple hydrophobic LLZO particles, multiple hydrophobic barium titanate particles, or multiple hydrophobic zinc oxide particles. The hydrophobic barium titanate particles or multiple hydrophobic zinc oxide particles coat the outer surface of the hydrophobic LLZO particles, forming multiple composite LLZO particles; in step C, the speed of the wet mixer is reduced to be lower than that in step B; wherein the above mixing and stirring... After mixing, the composite LLZO particles are formed. Each composite LLZO particle includes: an LLZO particle for guiding and dispersing lithium ions through the electrode; a hydroxide ion layer covering the outer surface of the LLZO particle; a dopamine layer covering the outside of the hydroxide ion layer of the LLZO particle, giving it primary hydrophobicity and further protecting the LLZO particle from moisture; and an outer hydrophobic layer covering the outer surface of the LLZO particle with the dopamine layer, forming the composite LLZO particle. The outer hydrophobic layer is composed of multiple hydrophobic barium titanate particles or hydrophobic zinc oxide particles or a combination of both. The hydroxide ion layer is coated around each barium titanate particle or zinc oxide particle, and a corresponding dopamine layer is coated around each of the particles.When the outer hydrophobic layer coats the outer surface of the hydrophobic LLZO particles, dopamine within the dopamine layer of each particle aggregates, thus forming the outer hydrophobic layer coating the outer surface of the hydrophobic LLZO particles. Tris(hydroxymethyl)amine can also be called tris(hydroxymethyl)aminomethane (Tris); tris(hydroxymethyl)amine hydrochloride can also be called tris(hydroxymethyl)aminomethane hydrochloride (Tris-HCl); and dopamine hydrochloride can also be called dopamine hydrochloride.

[0008] The present invention also includes step D: placing the third mixed slurry from step C into a vacuum thickener to remove most of the liquid and other unwanted residues, and then further drying it to evaporate the solvents such as methanol and hydrochloric acid (the hydrochloric acid is the product of the reaction of tris(hydroxymethyl)amine hydrochloric acid and dopamine hydrochloric acid) in the third mixed slurry to obtain the final powder.

[0009] The present invention also includes step E: placing the third mixed slurry and the alcohol solution containing carbon nanotubes into the wet mixer for mixing and stirring to form an LLZO particle slurry coated with carbon material.

[0010] This invention coats the LLZO material with a dopamine material, making it hydrophobic and thus preventing moisture from easily penetrating the LLZO material. Furthermore, carbon nanotubes and nanoscale amorphous carbon are added to the outer surface of the dopamine-coated LLZO material to coat the negative electrode particles in the battery's negative electrode material, thereby improving the overall conductivity of the negative electrode.

[0011] The features and advantages of the invention will be further understood from the following description, and please refer to the accompanying drawings while reading. Attached Figure Description

[0012] Figure 1 This invention is illustrated in the flowchart.

[0013] Figure 2 This shows a flowchart of step A of the present invention.

[0014] Figure 3 This shows a flowchart of step B of the present invention.

[0015] Figure 4 This shows a flowchart of step C of the present invention.

[0016] Figure 5 Examples of applications of the present invention are shown.

[0017] Figure 6 This diagram shows an enlarged view of the hydrophobic LLZO particle structure of the present invention, in which the OH- bonds of the dopamine form a dehydration polymerization reaction with the OH- bonds of the hydroxide ion layer.

[0018] Figure 7 This diagram shows an enlarged schematic of the hydrophobic barium titanate particle structure of the present invention.

[0019] Figure 8 This diagram shows an enlarged schematic of the hydrophobic zinc oxide particle structure of the present invention.

[0020] Figure 9 This diagram shows an enlarged schematic of the outer hydrophobic layer structure of the present invention.

[0021] Figure 10 This diagram shows a flowchart of another embodiment of the present invention.

[0022] Figure 11 This diagram shows the structure of the composite LLZO manufactured using the process of this invention.

[0023] Figure 12 This diagram shows the LLZO particle structure of the carbon-coated material of the present invention.

[0024] Figure 13 show Figure 11 Cross-sectional view. Detailed Implementation

[0025] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0026] Please refer to Figures 1 to 13 The diagram illustrates a method for manufacturing a protective coating electrode using composite ceramic electrolyte particles according to the present invention. The oxide ceramic particles are multiple composite LLZO (lithium lanthanum zirconium oxide) particles 100, primarily used in electrodes of solid-state or near-solid-state batteries, particularly the negative electrode 200 of such batteries. The LLZO is composed of lithium lanthanum zirconium oxide (Li7La3Zr2O). 12 Lithium lanthanum zirconium oxide (LLZO), or lithium lanthanum zirconium oxide doped with at least one metal element (e.g., Li 6.2 Ga 0.8 La3Zr2O 12 The composite LLZO particles 100 are gallium (Ga)-doped lithium lanthanum zirconium oxide (LLZO), or aluminum (Al)-doped or barium (Ba)-doped LLZO. The particle size of these composite LLZO particles 100 is between 50 nanometers and 200 nanometers. The proportions in the figures are not actual proportions and are intended only to illustrate the structure of the invention.

[0027] like Figure 5As shown, when used in the negative electrode 200 of the solid-state or solid-like battery, the negative electrode 200 comprises: a negative electrode substrate 210, which is a carrier material for supporting the negative electrode 200; and a negative electrode slurry layer 220 coated on the negative electrode substrate 210, the negative electrode slurry layer 220 comprising a negative electrode slurry 230 as a binder. The negative electrode slurry 230 may contain SBR (Styrene Butadiene Rubber), CMC (Carboxymethyl Cellulose), and a conductive agent (a mixture of carbon nanotubes or Super-P (conductive carbon)). The solvent used in the fabrication of the negative electrode slurry 230 is water. The negative electrode slurry layer 220 also contains a plurality of composite LLZO particles 100 for guiding lithium ions. Generally, the composite LLZO particles 100 account for 0.5 wt% to 5 wt% of the electrode slurry layer (especially the negative electrode slurry layer).

[0028] The manufacturing process of the composite LLZO particles 100 (please refer to...) Figures 1 to 4 The explanation is as follows:

[0029] Step A: Multiple LLZO particles 10, methanol 12 and hydrophobic material 17 are placed into a wet mixer 500 for mixing and grinding to form a first mixed slurry 15, wherein the hydrophobic material 17 is at least one of multiple barium titanate particles 21 or multiple zinc oxide particles 22 or a mixture thereof.

[0030] The particle size of each LLZO particle 10 is between 2 micrometers and 10 micrometers. The LLZO particle 10 has an irregular three-dimensional morphology. The particle size of each barium titanate particle 21 or zinc oxide particle 22 is between 10 nanometers and 20 nanometers. The outer surface of the LLZO particle 10 and the hydrophobic material 17 itself has oxidized functional groups.

[0031] The total weight ratio of the plurality of LLZO particles 10 to the methanol is 0.8 to 1.2:4. The total weight ratio of the hydrophobic material 17 to the total weight of the LLZO particles 10 is between 1 / 25 and 1 / 10 (4% to 10%), i.e., between 0.04 and 0.1.

[0032] The wet mixer 500 contains multiple zirconium beads 101 for mixing and grinding, resulting in LLZO particles 10 with a particle size of less than 500 nanometers. The wet mixer 500 operates at a speed of 2200 rpm ± 20%, the zirconium beads 101 have a particle size of 0.7 mm to 0.9 mm, a filling rate of 70% to 90%, a grinding time of 1 hour to 1.5 hours, and an operating temperature of 20℃ ± 4℃.

[0033] Step B: Tris(hydroxymethyl)aminomethane 13 and tris(hydroxymethyl)aminomethane hydrochloride 14 are added to the wet mixer 500 and further ground and stirred with the first mixed slurry 15 to form a second mixed slurry 20. Tris(hydroxymethyl)aminomethane 13 itself has three OH- bonds, two of which form hydrogen bonds with the oxidized functional groups on the surface of the LLZO particles 10 and the hydrophobic material 17. The third OH- bond of the tris(hydroxymethyl)aminomethane extends towards the outer surface of the LLZO particles 10 and the hydrophobic material 17 (e.g., ...). Figures 6 to 8 Therefore, a hydroxide ion (OH-) layer 24 is formed on the outer surface of both the LLZO particle 10 and the hydrophobic material 17. The thickness of the hydroxide ion layer 24 is between 0.5 nanometers and 2 nanometers. Only two tris(hydroxymethyl)amine molecules are shown in the figure; this number is for illustrative purposes only and is not intended to limit the scope of the invention.

[0034] The weight ratio of the tris(hydroxymethyl)amine 13 to the weight ratio of the tris(hydroxymethyl)amine hydrochloride 14 is 8:2.

[0035] In step B, after adding the tris(hydroxymethyl)amine 13 and the tris(hydroxymethyl)amine hydrochloride 14, the speed of the wet mixer 500 is increased to 2400 rpm ± 20%. This speed must be greater than the speed in step A. The grinding time is 0.5 hours, and the operating temperature is 20℃ ± 4℃.

[0036] The purpose of adding tris(hydroxymethyl)amine hydrochloride 14 is to control the pH value of the reaction. The reaction between LLZO particles 10 and tris(hydroxymethyl)amine 13 requires alkaline catalysis, but excessively high alkalinity can cause hydrolysis and deterioration of the LLZO particles 10. Therefore, adding tris(hydroxymethyl)amine hydrochloride 14 lowers the overall pH value, thus reducing alkalinity.

[0037] Step C: Add dopamine hydrochloride 25 to the wet mixer 500 and continue grinding and stirring with the second mixed slurry 20 from step B to form a third mixed slurry 30. The OH- bonds of the dopamine in the dopamine hydrochloride 25 will undergo a dehydration polymerization reaction with the OH- bonds of the hydroxide ion layer 24 coating the outer surface of the LLZO particles 10 and the hydrophobic material 17, while a copolymerization reaction will occur between the dopamine particles, thus forming a dopamine layer 35 coating the corresponding outer surface of the hydroxide ion layer 24 (e.g., ...). Figures 6 to 8The composite LLZO particles 102, 212, or 222 are formed by mixing multiple hydrophobic LLZO particles 102, multiple hydrophobic barium titanate particles 212, or multiple hydrophobic zinc oxide particles 222. These multiple hydrophobic barium titanate particles 212 or multiple hydrophobic zinc oxide particles 222 are then mixed and coated onto the hydrophobic LLZO particles 102, forming multiple composite LLZO particles 100 (e.g., ...). Figure 11 The thickness of the dopamine layer 35 is between 1 nanometer and 10 nanometers.

[0038] like Figure 9 , Figure 11 and Figure 13 As shown in the cross-sectional view, after the above mixing and stirring, composite LLZO particles 100 of the present invention are formed; wherein each composite LLZO particle 100 comprises: an LLZO particle 10 for guiding and dispersing lithium ions through the electrode; a hydroxide ion layer 24 covering the outer surface of the LLZO particle 10; and a dopamine layer 35 covering the outside of the hydroxide ion layer 24 to form the hydrophobic LLZO particle 102 (e.g., ...). Figure 6 The dopamine has hydrophobic properties, which can further protect the LLZO particles 10 from moisture; an outer hydrophobic layer 41 covers the outer surface of the hydrophobic LLZO particles 102, forming the composite LLZO particles 100 (e.g., ...). Figure 11 The outer hydrophobic layer 41 is a plurality of hydrophobic barium titanate particles 212 or a plurality of hydrophobic zinc oxide particles 222 or a combination thereof.

[0039] The barium titanate particles 21 or zinc oxide particles 22 are coated with a hydroxide ion layer 24; and each hydroxide ion layer 24 is further coated with a corresponding dopamine layer 35; when the outer hydrophobic layer 41 is coated on the outer surface of the hydrophobic LLZO particles 102, the dopamine in the dopamine layer of each particle will aggregate, so the outer hydrophobic layer 41 is coated on the outer surface of the hydrophobic LLZO particles 102, and the distribution of the barium titanate particles 21 or zinc oxide particles 22 is naturally formed during the process stirring.

[0040] The weight ratio of [the total weight of the LLZO particles 10] to [the tris(hydroxymethyl)amine 13 and the tris(hydroxymethyl)amine hydrochloride 14] to [the dopamine hydrochloride 25] is 1:0.8 to 1:2.2 to 2.4.

[0041] In step C, the speed of the wet mixer 500 is reduced to 2000 rpm ± 20% (this speed must be less than the speed in step B), the grinding time is 0.5 hours to 1 hour, and the operating temperature is 20℃ ± 4℃.

[0042] Because moisture is present during the manufacturing process of this electrode, and the LLZO particles 10 are hydrophilic and therefore easily absorb moisture, producing alkaline substances, a protective layer must be applied to the outer layer of the LLZO particles 10 to prevent them from absorbing moisture during the electrode manufacturing process. Since dopamine has hydrophobic properties, dopamine hydrochloride 25 is added in step C to further coat the LLZO particles 10 and prevent them from absorbing moisture.

[0043] Step D: The third mixed slurry 30 from step C is placed in a vacuum concentrator 550 to remove most of the methanol 12 and other unwanted residues. It can then be further dried to evaporate the methanol 12, hydrochloric acid and other solvents in the third mixed slurry 30, resulting in a final powder.

[0044] Step C can be followed by step E, and then step D, which involves reduced pressure concentration. For example... Figure 10 As shown, step E is explained as follows:

[0045] Step E: The third mixed slurry 30 and the alcohol solution 45 containing carbon nanotubes (CNTs) are placed in the wet mixer and mixed and stirred, so that each composite LLZO particle 100 is coated with multiple carbon nanotubes 42, forming a carbon-coated LLZO particle slurry 40. The carbon-coated LLZO particles are in the shape of yarn balls (e.g., Figure 12 The preferred alcohol solution is a methanol solution.

[0046] In step E, the wet mixer 500 operates at a speed of 2000 rpm ± 20%, a grinding time of 0.5 hours, and an operating temperature of 20 ± 4℃.

[0047] In this invention, the length of the carbon nanotube 42 is between 0.5 micrometers and 3 micrometers; the weight ratio of the carbon nanotube-containing alcohol solution 45 to the third mixed slurry 30 is 0.01 to 0.5:100.

[0048] After the above-mentioned processes from steps A to D, the composite LLZO particles 100 have a size of 50 nanometers to 200 nanometers.

[0049] Carbon nanotubes are used to increase electronic conductivity by forming conductive bridges around the various composite LLZO particles 100, allowing electrons to conduct through the composite LLZO particles 100. Because carbon nanotubes have extremely high conductivity, lithium ions can be conducted between different composite LLZO particles 100 through the carbon nanotubes, thus increasing the overall conductivity of the electrode.

[0050] In step E of this invention, nanoscale amorphous carbon 48 may also be added to the alcohol solution 45 containing carbon nanotubes, wherein the size of the nanoscale amorphous carbon 48 is between 10 nanometers and 40 nanometers. This nanoscale amorphous carbon 48 is, for example, a super P conductive agent. Like the carbon nanotubes 42, the nanoscale amorphous carbon 48 is a conductive agent. Because the nanoscale amorphous carbon 48 is in the form of particles, while the carbon nanotubes 42 are in the form of elongated strips, gaps are formed between the crisscrossing carbon nanotubes 42. These gaps cannot conduct current. Therefore, adding the nanoscale amorphous carbon 48 into these gaps allows charge to be conducted to the next carbon nanotube 42 through the bridging of the nanoscale amorphous carbon 48, thus further increasing current transfer.

[0051] The advantage of this invention is that it breaks down the traditional single-step mixing process into multiple mixing and grinding steps. This results in a longer reaction time and finer LLZO particles with a larger surface area. Therefore, the LLZO particles can effectively and fully react with tris(hydroxymethyl)amine and dopamine hydrochloride, thus forming a more robust external dopamine layer. Furthermore, multiple hydrophobic barium titanate particles or multiple hydrophobic zinc oxide particles are coated on the outer surface of the dopamine-coated LLZO particles, providing further hydrophobic protection. Therefore, the entire composite LLZO particle structure has enhanced lithium conductivity, and it avoids reactions with water during electrode manufacturing, achieving better battery electrode material manufacturing quality.

[0052] In summary, the human-centered and considerate design of this invention is highly suitable for practical needs. Its specific improvements over existing deficiencies represent a significant breakthrough compared to conventional technology, offering substantial efficiency gains that are not easily achieved.

[0053] The above detailed description is a specific description of a feasible embodiment of the present invention. However, this embodiment is not intended to limit the patent scope of the present invention. All equivalent implementations or modifications that do not depart from the spirit of the present invention should be included in the patent scope of the present invention.

Claims

1. A method for manufacturing composite ceramic electrolyte particles for electrodes with a protective coating, characterized in that, The composite ceramic electrolyte particles are multiple composite LLZO particles, wherein LLZO is lithium lanthanum zirconium oxide or lithium lanthanum zirconium oxide doped with at least one metal element; the process of fabricating the electrode with the hydrophobic protective layer using the composite ceramic electrolyte particles includes the following steps: Step A: Place multiple LLZO particles, methanol, and hydrophobic material into a wet mixer for mixing and grinding to form a first mixed slurry, wherein the hydrophobic material is at least one of multiple barium titanate particles or multiple zinc oxide particles, or a mixture thereof. The wet mixer contains multiple zirconium beads for mixing and grinding, resulting in LLZO particles with a particle size of less than 500 nanometers. Step B: Tris(hydroxymethyl)amine and tris(hydroxymethyl)amine hydrochloride are added to the wet mixer and ground and stirred with the first mixed slurry to form a second mixed slurry. Tris(hydroxymethyl)amine itself has three OH- bonds, two of which will form hydrogen bonds with the oxidative functional groups on the surface of the LLZO particles and the hydrophobic material; while the third OH- bond of tris(hydroxymethyl)amine will extend towards the outer surface of the LLZO particles and the hydrophobic material, thus forming a hydroxide ion layer on the outer surface of the LLZO particles and the hydrophobic material. In step B, after adding the tris(hydroxymethyl)amine and the tris(hydroxymethyl)amine hydrochloride, the speed of the wet mixer is increased; this speed must be greater than the speed in step A. Step C: Add dopamine hydrochloric acid to the wet mixer and continue grinding and stirring with the second mixed slurry from Step B to form a third mixed slurry; wherein the OH- bonds of dopamine itself in the dopamine hydrochloric acid will undergo a dehydration polymerization reaction with the OH- bonds of the hydroxide ion layer coating the LLZO particles and the hydrophobic material, so that dopamine can combine with the LLZO particles and the hydrophobic material. Since the dopamine will undergo a copolymerization reaction, a dopamine layer is formed, which in turn forms multiple hydrophobic LLZO particles, multiple hydrophobic barium titanate particles or multiple hydrophobic zinc oxide particles. The hydrophobic barium titanate particles or multiple hydrophobic zinc oxide particles will coat the outer surface of the hydrophobic LLZO particles to form multiple composite LLZO particles; In step C, the rotational speed of the wet mixer is reduced to be less than that in step B; The above-mentioned mixing and stirring process forms the composite LLZO particles. Each composite LLZO particle comprises: an LLZO particle for guiding and dispersing lithium ions through the electrode; a hydroxide ion layer covering the outer surface of the LLZO particle; a dopamine layer covering the outside of the hydroxide ion layer of the LLZO particle, giving it primary hydrophobicity and further protecting the LLZO particle from moisture; and an outer hydrophobic layer covering the outer surface of the hydrophobic LLZO particle, forming the composite LLZO particle; wherein the outer hydrophobic layer is composed of multiple hydrophobic barium titanate particles or hydrophobic zinc oxide particles or a combination of both. The outer periphery of each barium titanate particle or zinc oxide particle is coated with a hydroxide ion layer; and a corresponding dopamine layer is coated on the outer periphery of each particle. When the outer hydrophobic layer is coated on the outer surface of the hydrophobic LLZO particle, the dopamine in the dopamine layer of each particle will aggregate. Therefore, the outer hydrophobic layer is coated on the outer surface of the hydrophobic LLZO particle, and the whole is formed into the composite LLZO particle.

2. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, It also includes step D: placing the third mixed slurry from step C into a vacuum thickener to remove most of the liquid and other unwanted residues, and then further drying it to evaporate the methanol and hydrochloric acid solvents in the third mixed slurry to obtain the final powder.

3. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1 or 2, characterized in that, It also includes step E: placing the third mixed slurry and the carbon nanotube-containing alcohol solution into the wet mixer for mixing and stirring to form a carbon-coated LLZO particle slurry.

4. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 3, characterized in that, In step E, nanoscale amorphous carbon, with a size between 10 nanometers and 40 nanometers, is also added to the alcohol solution containing carbon nanotubes.

5. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 3, characterized in that, The length of the carbon nanotubes ranges from 0.5 micrometers to 3 micrometers.

6. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 3, characterized in that, in The total weight ratio of the multiple LLZO particles to the methanol is 0.8 to 1.2:4; The weight ratio of the total weight of the hydrophobic material to the total weight of the LLZO particles is between 0.04 and 0.

1. The weight ratio of the carbon nanotube-containing alcohol solution to the third mixed slurry is 0.01 to 0.5:

100.

7. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, This is the negative electrode used in solid-state or solid-state-like batteries.

8. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, After the above-mentioned processes from steps A to D, the composite LLZO particles have a size of 50 nanometers to 200 nanometers and exhibit an irregular three-dimensional morphology.

9. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, in, In step B, the weight ratio of the tris(hydroxymethyl)amine to the tris(hydroxymethyl)amine hydrochloride is 8:

2. In step C, the weight ratio of [the total weight of the LLZO particles] to [the tris(hydroxymethyl)amine and tris(hydroxymethyl)amine hydrochloride] to [the dopamine hydrochloride] is 1:0.8 to 1:2.2 to 2.

4.

10. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, In step C, the thickness of the dopamine layer is between 1 nanometer and 10 nanometers.

11. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 1, characterized in that, in, In step A, the rotation speed of the wet mixer is 2200 rpm ± 20%, the particle size of the zirconium beads is 0.7 mm to 0.9 mm, the zirconium bead filling rate is 70% to 90%, the grinding time is 1 hour to 1.5 hours, and the operating temperature is 20℃ ± 4℃. In step B, after adding the tris(hydroxymethyl)amine and the tris(hydroxymethyl)amine hydrochloride, the speed of the wet mixer is increased to 2400 rpm ± 20%, the grinding time is 0.5 hours, and the operating temperature is 20℃ ± 4℃. In step C, the rotation speed of the wet mixer is reduced to 2000 rpm ± 20%, the grinding time is 0.5 hours to 1 hour, and the operating temperature is 20℃ ± 4℃.

12. The method for manufacturing a protective-coated electrode using composite ceramic electrolyte particles according to claim 3, characterized in that, in, In step E, the wet mixer operates at a speed of 2000 rpm ± 20%, a grinding time of 0.5 hours, and an operating temperature of 20 ± 4℃.

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