Method for manufacturing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer

Abstract

This invention provides a method for manufacturing composite ceramic electrolyte particles for battery electrodes that are coated with a hydrophobic protective layer. [Solution] The method includes: step A, which involves putting a plurality of first LLZO particles, methanol, and a plurality of hydrophobic particles into a wet mixer and mixing and polishing them; step B, which involves adding tris(hydroxymethyl)aminomethane and tris(hydroxymethyl)aminomethane hydrochloride to the wet mixer and continuously stirring to form a hydroxide ion layer on the outer surface of the first LLZO particles and the hydrophobic particles; and step C, which involves adding dopamine hydrochloride to the wet mixer and continuously polishing and stirring to cause a dehydration polymerization reaction between the dopamine molecules of the dopamine hydrochloride and the hydroxide ion layer, and causing aggregation between the dopamine molecules, thereby forming a dopamine layer that coats the outside of the hydroxide ion layer of the corresponding first LLZO particles or hydrophobic particles. The hydrophobic particles having the dopamine layer coat the first LLZO particles having the dopamine layer, forming composite LLZO particles.

Description

[Technical Field]

[0001] The present invention relates to battery electrode materials, and more particularly to a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer. [Background technology]

[0002] Batteries are primarily formed by placing a positive electrode and a negative electrode in an electrolyte. In conventional technology, the ionic conductivity is increased by adding LLZO material to the negative electrode. Because LLZO material has high ionic conductivity for lithium ions, when lithium ions pass through the negative electrode, the dispersed LLZO particles act as guides, dispersing the lithium ion pathways. This ensures that lithium ions are distributed uniformly within the negative electrode, preventing abnormal accumulation of lithium ions in the negative electrode slurry and thus preventing side reactions with the slurry. [Overview of the Initiative] [Problems that the invention aims to solve]

[0003] However, in the conventional technology described above, moisture is present during the manufacturing process of the negative electrode, and because the LLZO material is hydrophilic, the LLZO material reacts easily with water, and when it gets wet, alkaline substances are generated, causing the material of the negative electrode slurry to deteriorate.

[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. Specifically, the main objective of this invention is to provide a method for producing composite ceramic electrolyte particles for battery electrodes that are coated with a hydrophobic protective layer. [Means for solving the problem]

[0006] To solve the above problems, a method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer according to a certain aspect of the present invention is provided, wherein the composite ceramic electrolyte particles are a plurality of composite LLZO particles, and the production method is Step A involves adding a plurality of first LLZO particles, methanol, and a plurality of hydrophobic particles to a wet mixer and mixing and polishing them at a first rotation speed to form a first mixed slurry, wherein the plurality of hydrophobic particles are formed by a plurality of barium titanate particles, a plurality of zinc oxide particles, or a combination thereof, and adding a plurality of zirconium beads to the wet mixer and mixing and polishing them to make the particle size of each of the first LLZO particles 10 less than 500 nm. Tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2) and tris(hydroxymethyl)aminomethane hydrochloride (NH2C(CH2OH)3·HCl) are added to the wet mixer and polished and stirred with the first mixed slurry to form a second mixed slurry, and the outer surfaces of each of the first LLZO particles and each of the hydrophobic particles are coated with hydroxide ion layers, and the tris(hydroxymethyl)aminomethane is first OH - Ion, 2OH - Ions, and 3OH - The three OH groups of ions - Having an ion, the first OH - Ions and the aforementioned 2OH - The ions are bonded by hydrogen bonding forces with the oxidative functional groups of the first LLZO particles or hydrophobic particles, and the third OH - By extending the ions toward the outer surface of the first LLZO particles or hydrophobic particles, a corresponding hydroxide ion layer is formed that covers the outer surface of the corresponding first LLZO particles or hydrophobic particles, and the hydroxide ion layer comprises a plurality of corresponding third OH - Step B, which involves ions, In the step B, after adding the tris(hydroxymethyl)aminomethane and the tris(hydroxymethyl)aminomethane hydrochloride, the rotation speed of the wet mixer is increased to a second rotation speed for polishing and stirring. That is, the second rotation speed is faster than the first rotation speed in the step A, and the step B, By adding dopamine hydrochloride to the wet mixer and polishing and stirring to form a third mixed slurry having a plurality of the composite LLZO particles, the OH of the dopamine molecule of the dopamine hydrochloride - Ions are the third OH of the hydroxide ion layer of each of the first LLZO particles and each of the hydrophobic particles - Generate a dehydration polymerization reaction (polymerization triggered by dehydration) with the ions, and bind each of the first LLZO particles and each of the hydrophobic particles to a corresponding plurality of dopamine molecules respectively, and cause a copolymerization reaction between these corresponding plurality of dopamine molecules to form a dopamine layer covering the outer surface of the hydroxide ion layer of the corresponding first LLZO particle or hydrophobic particle. A plurality of the first LLZO particles covered by the dopamine layer form a plurality of hydrophobic LLZO particles. When the hydrophobic particle is the barium titanate particle, the hydrophobic particle covered by the dopamine layer forms a hydrophobic barium titanate composite particle. When the hydrophobic particle is the zinc oxide particle, the hydrophobic particle covered by the dopamine layer forms a hydrophobic zinc oxide composite particle. The hydrophobic barium titanate composite particle or the hydrophobic zinc oxide composite particle covers the hydrophobic LLZO particle, which is the step C of forming the composite LLZO particle, In the step C, the rotation speed of the wet mixer is decreased to a third rotation speed. That is, the third rotation speed is slower than the second rotation speed in the step B, and the step C, is included, Each of the composite LLZO particles formed in step C comprises a first LLZO particle for guiding and dispersing lithium ions passing through the electrode, the outer surface of the first LLZO particle is coated with a corresponding hydroxide ion layer, and the outside of the hydroxide ion layer is coated with a corresponding dopamine layer to form the hydrophobic LLZO particle, the dopamine molecules in the dopamine layer are hydrophobic and therefore further protect the first LLZO particle, the outer hydrophobic layer coats the outer surface of the hydrophobic LLZO particle to form the composite LLZO particle, the outer hydrophobic layer is formed by a plurality of corresponding hydrophobic barium titanate composite particles, a plurality of corresponding hydrophobic zinc oxide composite particles, or a combination thereof. Each barium titanate particle in the hydrophobic barium titanate composite particles and each zinc oxide particle in the hydrophobic zinc oxide composite particles are coated with a corresponding hydroxide ion layer, and the hydroxide ion layer of the barium titanate particles and the zinc oxide particles are coated with a corresponding dopamine layer. The dopamine molecules in the dopamine layer of the hydrophobic LLZO particles and the dopamine molecules in the dopamine layer of the outer hydrophobic layer undergo a chain copolymerization reaction, causing the outer hydrophobic layer to coat the outer surface of the hydrophobic LLZO particles. [Effects of the Invention]

[0007] This invention divides the conventional single-step mixing process into multiple mixing and polishing steps, extending the overall reaction time. Furthermore, by making the LLZO particles smaller and increasing their surface area, the LLZO particles react sufficiently with tris(hydroxymethyl)aminomethane and dopamine hydrochloride, forming a solid dopamine layer on the surface of the LLZO particles. In addition, the outer surface of the LLZO particles covered by the dopamine layer is further coated with multiple hydrophobic barium titanate composite particles or hydrophobic zinc oxide composite particles to form an even more suitable hydrophobic protective structure. As a result, the entire composite LLZO particle has enhanced lithium-ion guiding ability, does not react with water during the electrode manufacturing process, and achieves even better manufacturing quality for battery electrode materials.

[0008] Other features of the present invention will be made clearer by description in this specification and the accompanying drawings. [Brief explanation of the drawing]

[0009] [Figure 1] This is a flowchart showing a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to one embodiment of the present invention. [Figure 2] This is a schematic flowchart showing step A of a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to one embodiment of the present invention. [Figure 3] This is a schematic flowchart showing step B of a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to one embodiment of the present invention. [Figure 4] This flowchart schematically shows steps C and D of a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to one embodiment of the present invention. [Figure 5] An example of a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to one embodiment of the present invention is shown. [Figure 6]It is a schematic configuration diagram showing the configuration of hydrophobic LLZO particles and the configuration of its parts according to an embodiment of the present invention, and a dehydration copolymerization reaction is formed by the OH-ions of dopamine molecules and the third OH-ion of the hydroxide ion layer. [Figure 7] It is a schematic diagram showing the configuration of hydrophobic barium titanate composite particles and the configuration of its parts according to an embodiment of the present invention. [Figure 8] It is a schematic diagram showing the configuration of hydrophobic zinc oxide composite particles and the configuration of its parts according to an embodiment of the present invention. [Figure 9] It is a schematic diagram showing the partial configuration of the outer hydrophobic layer according to an embodiment of the present invention. [Figure 10] It is a flowchart showing a method for manufacturing composite ceramic electrolyte particles for a battery electrode coated with a hydrophobic protective layer according to another embodiment of the present invention. [Figure 11] It is a schematic diagram showing the configuration applied to composite LLZO particles according to an embodiment of the present invention. [Figure 12] It is a schematic diagram showing the configuration of composite LLZO particles coated with a carbon material according to an embodiment of the present invention. [Figure 13] It is a cross-sectional view along FIG. 11. [Figure 14] It is another flowchart schematically showing steps C and D according to an embodiment of the present invention.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Needless to say, the present invention is not limited to the following examples and can be arbitrarily changed without departing from the gist of the present invention.

[0011] First, a method for manufacturing composite ceramic electrolyte particles for a battery electrode coated with a hydrophobic protective layer according to the present invention will be described while referring to FIGS. 1 to 14. The present invention relates to a method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer. The oxide ceramic particles are a plurality of composite LLZO particles 100, which are mainly used in electrodes of solid or semi-solid batteries, and in particular in the negative electrode 200 of the solid or semi-solid battery. The particle size of each of the composite LLZO particles 100 is in the range of 50 nm to 200 nm. The size ratios in the figures are used only to illustrate the structure of the present invention and do not represent the actual ratios. As shown in Figure 5, the plurality of composite LLZO particles 100 are used in the negative electrode 200 of the solid or semi-solid battery. The negative electrode 200 comprises a negative electrode substrate 210, which is a substrate on which the material of the negative electrode 200 is placed, 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 and a plurality of composite LLZO particles 100 for guiding lithium ions. The negative electrode slurry 230 is a mixture of SBR (Styrene Butadiene Rubber), CMC (Carboxymethyl Cellulose), and a conductive agent (carbon nanotube or Super-P (conductive carbon black)). The solvent used in the production of the negative electrode slurry 230 is water. The weight percentage of the multiple composite LLZO particles 100 in the electrode slurry layer (particularly the negative electrode slurry layer) is in the range of 0.5 wt% to 5 wt%.

[0012] Next, an example of the manufacturing process for the multiple composite LLZO particles 100 of the present invention will be described with reference to Figures 1 to 4.

[0013] <Process A> Multiple first LLZO particles 10, methanol 12, and multiple hydrophobic particles 17 are placed in a wet mixer 500 and mixed and polished at a first rotation speed to form a first mixed slurry 15. The multiple hydrophobic particles 17 are formed from multiple barium titanate particles 21, multiple zinc oxide particles 22, or a combination of both.

[0014] The particle size of each of the first LLZO particles 10 is in the range of 2 μm to 10 μm. The first LLZO particles 10 exhibit an irregular three-dimensional shape. The particle size of the barium titanate particles 21 or the zinc oxide particles 22 is in the range of 10 nm to 20 nm. The outer surfaces of the first LLZO particles 10 and the hydrophobic particles 17 have oxidative functional groups.

[0015] Each of the first LLZO particles 10 is formed of lithium lanthanum zirconium oxide (Li7La3Zr2O12, LLZO) or lithium lanthanum zirconium oxide doped with at least one metal element (for example, Li 6.2 Ga 0.8 La3Zr2O 12 This may be a gallium (Ga)-doped lithium lanthanum zirconate compound, or an aluminum (Al) or barium (Ba)-doped lithium lanthanum zirconate compound.

[0016] The weight ratio of the total weight of the multiple first LLZO particles 10 to the methanol 12 is in the range of 0.8 to 1.2:4. The weight ratio of the total weight of the multiple hydrophobic particles 17 to the total weight of the multiple first LLZO particles 10 is in the range of 1 / 25 to 1 / 10 (4% to 10%).

[0017] Multiple zirconium beads 101 are placed in the wet mixer 500 and mixed and polished. The particle size of each of the first LLZO particles 10 is less than 500 nm, the first rotational speed of the wet mixer 500 is 2200 rpm ± 20%, and the particle size of the zirconium beads 101 is in the range of 0.7 mm to 0.9 mm. The packing rate of the total volume of the multiple zirconium beads 101 is in the range of 70% to 90%, which is the ratio of the total volume of the multiple first zirconium beads 101 to the polishing volume of the wet mixer 500. The polishing time is in the range of 1 hour to 1.5 hours, and the operating temperature is 20°C ± 4°C.

[0018] <Process B> Tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2)13 and tris(hydroxymethyl)aminomethane hydrochloride (NH2C(CH2OH)3·HCl)14 are added to the wet mixer 500 and polished and stirred with the first mixed slurry 15 to form a second mixed slurry 20, and the outer surfaces of each of the first LLZO particles 15 and each of the hydrophobic particles 17 are coated with hydroxide ions (OH - Each is coated with layer 24. The tris(hydroxymethyl)aminomethane is the first OH - Ion, 2OH - Ions, and 3OH - The three OH groups of ions - Having an ion, the first OH - Ions and the aforementioned 2OH - The ions are bonded to the oxidative functional groups of the first LLZO particles 10 or hydrophobic particles 17 by hydrogen bonding forces. - By extending the ions toward the outer surface of the first LLZO particle 10 or hydrophobic particle 17 (see Figures 6 to 8), a corresponding hydroxide ion layer 24 is formed that covers the outer surface of the corresponding first LLZO particle 10 or hydrophobic particle 17. The hydroxide ion layer 24 is made up of multiple corresponding third OH - It contains ions. The thickness of the hydroxide ion layer 24 is in the range of 0.5 nm to 2 nm. Only two tris(hydroxymethyl)aminomethane molecules are shown in the drawing for illustrative purposes, but this does not limit the scope of the present invention.

[0019] The weight ratio of the tris(hydroxymethyl)aminomethane 13 to the tris(hydroxymethyl)aminomethane hydrochloride 14 is 8:2.

[0020] In step B, the tris(hydroxymethyl)aminomethane 13 and the tris(hydroxymethyl)aminomethane hydrochloride 14 are added, and then the rotation speed of the wet mixer 500 is increased to the second rotation speed for polishing and stirring, i.e., the second rotation speed is faster than the first rotation speed in step A. The second rotation speed is 2400 rpm ± 20%, the polishing time is 0.5 hours, and the operating temperature is 20°C ± 4°C.

[0021] The purpose of adding the tris(hydroxymethyl)aminomethane hydrochloride 14 is to control the pH value of the chemical reaction. The reaction between the first LLZO particles 10 and the tris(hydroxymethyl)aminomethane 13 requires catalytic activity in an alkaline environment, but if the alkalinity is too high, the first LLZO particles 10 will be hydrolyzed and deteriorate. Therefore, by adding the tris(hydroxymethyl)aminomethane hydrochloride 14, the overall pH value is lowered, thereby reducing the alkalinity during the reaction.

[0022] <Process C> Dopamine hydrochloride 25 is added to the wet mixer 500 and polished and stirred with the second mixed slurry 20 to form a third mixed slurry 30 having a plurality of the composite LLZO particles 100. The OH of the dopamine molecule of the dopamine hydrochloride 25 - The ions are the third OH of the hydroxide ion layer 24 of each of the first LLZO particles 10 and each of the hydrophobic particles 17 -A dehydration polymerization reaction (polymerization triggered by dehydration) is generated with ions to bind each of the first LLZO particles 10 and each of the hydrophobic particles 17 to a corresponding plurality of dopamine molecules, and a copolymerization reaction is generated between these corresponding plurality of dopamine molecules to form a dopamine layer 35 that covers the outer surface of the hydroxide ion layer 24 of the corresponding first LLZO particles 10 or hydrophobic particles 17 (see Figures 6 to 8). A plurality of hydrophobic LLZO particles 102 are formed from a plurality of first LLZO particles 10 coated with the dopamine layer 35. If the hydrophobic particle 17 is the barium titanate particle 21, the hydrophobic particle 17 coated with the dopamine layer 35 forms a hydrophobic barium titanate composite particle 212. If the hydrophobic particle 17 is the zinc oxide particle 22, the hydrophobic particle 17 coated with the dopamine layer 35 forms a hydrophobic zinc oxide composite particle 222. The hydrophobic LLZO particles 102 are coated with the hydrophobic barium titanate composite particles 212 or hydrophobic zinc oxide composite particles 222 to form the composite LLZO particles 100 (see Figure 11). The thickness of the dopamine layer 35 is in the range of 1 nm to 10 nm.

[0023] As shown in the cross-sectional views of Figures 9, 11, and 13, a plurality of composite LLZO particles 100 are formed through the above-mentioned process C. Each of the composite LLZO particles 100 is a first LLZO particle 10 that guides and disperses lithium ions passing through the electrode, the outer surface of the first LLZO particle 10 is coated with a corresponding hydroxide ion layer 24, and the outside of the hydroxide ion layer 24 is coated with a corresponding dopamine layer 35 to form the hydrophobic LLZO particle 102 (see Figure 6), the dopamine molecules of the dopamine layer 35 are hydrophobic and further protect the first LLZO particle 10 from getting wet, and an outer hydrophobic layer 41 that covers the outer surface of the hydrophobic LLZO particle 102 and forms the composite LLZO particle 100 (see Figure 11), the outer hydrophobic layer 41 is formed by a plurality of corresponding hydrophobic barium titanate composite particles 212, a plurality of corresponding hydrophobic zinc oxide composite particles 222, or a combination thereof.

[0024] Each barium titanate particle 21 of the hydrophobic barium titanate composite particles 212 and each zinc oxide particle 22 of the hydrophobic zinc oxide composite particles 222 are coated with a corresponding hydroxide ion layer 24, and the hydroxide ion layer 24 of the barium titanate particles 21 and the zinc oxide particles 22 are coated with a corresponding dopamine layer 35. The dopamine molecules of the dopamine layer 35 of the hydrophobic LLZO particles 102 and the dopamine molecules of the dopamine layer 35 of the outer hydrophobic layer 41 undergo a chain copolymerization reaction, causing the outer hydrophobic layer 41 to coat the outer surface of the hydrophobic LLZO particles 102. The distribution of the barium titanate particles 21 or zinc oxide particles 22 is formed naturally during stirring in the process.

[0025] The weight ratio of the total weight of the multiple first LLZO particles 10, the total weight of the tris(hydroxymethyl)aminomethane 13 and the tris(hydroxymethyl)aminomethane hydrochloride 14, and the weight of the dopamine hydrochloride 25 is in the range of 1:0.8 to 1:2.2 to 2.4.

[0026] In step C, the rotational speed of the wet mixer 500 is reduced to a third rotational speed. That is, the third rotational speed is slower than the second rotational speed in step B, the third rotational speed is 2000 rpm ± 20%, the polishing time is in the range of 0.5 hours to 1 hour, and the operating temperature is 20°C ± 4°C.

[0027] During the manufacturing process of the electrode, moisture is present, and because the first LLZO particles 10 are hydrophilic, they tend to get wet and generate alkaline substances. Therefore, it is necessary to coat the outside of the first LLZO particles 10 with a protective layer to prevent them from getting wet during the manufacturing process of the electrode. Since dopamine is hydrophobic, in step C, the dopamine hydrochloride 25 is added so that the dopamine further coats the first LLZO particles 10, preventing them from getting wet.

[0028] <Process D> In step C, the third mixed slurry 30 is introduced into a rotary evaporator 550 to remove most of the methanol 12 and other unwanted residues, and then dried to evaporate the methanol 12, hydrochloric acid and other solvents from the third mixed slurry 30 to obtain the final powder.

[0029] As shown in Figures 10 and 14, the process C further includes a sub-process E, which will be described below. Sub-step E: After forming the third mixed slurry 30, an alcohol-based solution 45 containing a plurality of carbon nanotubes (CNTs) 42 is added to the wet mixer 500 and mixed and stirred with the third mixed slurry 30, so that the outer surface of each of the composite LLZO particles 100 is coated with a plurality of corresponding carbon nanotubes 42, thereby forming composite LLZO particles 100 that coat a carbon material exhibiting a ball-like shape (see Figure 12). The alcohol-based solution is preferably a methanol solution.

[0030] In the sub-step E, the alcohol-based solution 45 is added, and then the wet mixer is used to continuously polish the material for 0.5 hours at a rotational speed of 2000 rpm ± 20%, while maintaining an operating temperature of 20 ± 4°C.

[0031] The length of the carbon nanotube 42 is in the range of 0.5 μm to 3 μm, and the weight ratio of the alcohol-based solution 45 to the third mixed slurry 30 is in the range of 0.01 to 0.5:100.

[0032] After going through process D, the size of the composite LLZO particles 100 is in the range of 50 nm to 200 nm and exhibits an irregular three-dimensional shape.

[0033] Carbon nanotubes are used to enhance electron conductivity by forming conductive bridges around the various composite LLZO particles 100, thereby enabling electron conduction on the composite LLZO particles 100. Carbon nanotubes have extremely high conductivity, and the carbon nanotubes 42 conduct lithium ions between the different composite LLZO particles 100, thereby enhancing the overall conductivity of the electrode.

[0034] The alcohol-based solution 45 further contains a plurality of nanoscale amorphous carbon 48, each nanoscale amorphous carbon 48 having a size in the range of 10 nm to 40 nm. Each of the nanoscale amorphous carbon 48 is, for example, an amorphous carbon of a super P conductive agent. Both the nanoscale amorphous carbon 48 and the carbon nanotubes 42 are conductive agents. The nanoscale amorphous carbon 48 exhibits a particle form, and the plurality of carbon nanotubes 42 exhibit an elongated form, with gaps formed between different carbon nanotubes 42 intersecting vertically and horizontally. The plurality of nanoscale amorphous carbon 48 fill these gaps, and the charge is conducted to the next carbon nanotube 42 by the nanoscale amorphous carbon 48 spanning across them, thus further accelerating the transmission of electric current.

[0035] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Explanation of symbols]

[0036] 10. First LLZO particle 12 methanol 13 Tris(hydroxymethyl)aminomethane 14 Tris(hydroxymethyl)aminomethane hydrochloride 15. First mixed slurry 17 Hydrophobic particles 20. Second mixed slurry 21 Barium titanate particles 22 Zinc Oxide Particles 24. Hydroxide ion layer 25. Dopamine hydrochloride 30. Third mixed slurry 35 Dopamine layer 41 Outer hydrophobic layer 42 Carbon nanotubes 45. Alcohol-based solutions 48 Nanoscale amorphous carbon 100 composite LLZO particles 101 Zirconium Beads 102 Hydrophobic LLZO particles 200 negative electrode 210 Negative electrode substrate 211 Hydrophobic barium titanate composite particles 220 Negative electrode slurry layer 222 Hydrophobic zinc oxide composite particles 230 Negative electrode slurry 500 Wet Mixer 550 Rotary Evaporator

Claims

1. A method for manufacturing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer, wherein the composite ceramic electrolyte particles are a plurality of composite LLZO particles, and the manufacturing method is: Step A involves introducing a plurality of first LLZO particles, methanol, and a plurality of hydrophobic particles into a wet mixer and mixing and polishing them at a first rotational speed to form a first mixed slurry, wherein the plurality of hydrophobic particles are formed by a plurality of barium titanate particles, a plurality of zinc oxide particles, or a combination thereof, and introducing a plurality of zirconium beads into the wet mixer and mixing and polishing them to make the particle size of each of the first LLZO particles 10 less than 500 nm. Tris(hydroxymethyl)aminomethane (tris(hydroxymethyl)aminomethane, (HOCH 2 )) 3 CNH 2 ) and tris(hydroxymethyl)aminomethane hydrochloride (tris(hydroxymethyl)aminomethane hydrochloride, NH 2 C(CH 2 OH) 3 ·HCl) are added to the wet mixer and the first mixed slurry is polished and stirred to form a second mixed slurry. The outer surfaces of each of the first LLZO particles and each of the hydrophobic particles are each coated with a hydroxide ion layer. The tris(hydroxymethyl)aminomethane has three OH - ions, namely the first OH - ion, the second OH - ion, and the third OH - ion. The first OH - ion and the second OH - ion are bonded by the hydrogen bonding interaction force with the oxidation functional group of the first LLZO particle or hydrophobic particle. By extending the third OH - ion toward the outer surface of the first LLZO particle or hydrophobic particle, a corresponding hydroxide ion layer covering the outer surface of the corresponding first LLZO particle or hydrophobic particle is formed. The hydroxide ion layer contains a plurality of corresponding third OH - ions in step B In step B, after adding the tris(hydroxymethyl)aminomethane and the tris(hydroxymethyl)aminomethane hydrochloride, the rotation speed of the wet mixer is increased to the second rotation speed for polishing and stirring, that is, the second rotation speed is faster than the first rotation speed in step A. By adding dopamine hydrochloride to the wet mixer and polishing and stirring it with the second mixed slurry, a third mixed slurry having a plurality of the composite LLZO particles is formed, and the OH of the dopamine molecule of the dopamine hydrochloride - The ions are in the third OH of the hydroxide ion layer of each of the first LLZO particles and each of the hydrophobic particles. - Step C involves generating a dehydration polymerization reaction with ions to bind each of the first LLZO particles and each of the hydrophobic particles to a corresponding plurality of dopamine molecules, generating a copolymerization reaction between these corresponding plurality of dopamine molecules to form a dopamine layer that covers the outer surface of the hydroxide ion layer of the corresponding first LLZO particle or hydrophobic particle, the plurality of first LLZO particles covered by the dopamine layer form a plurality of hydrophobic LLZO particles, if the hydrophobic particle is the barium titanate particle, the hydrophobic particle covered by the dopamine layer forms a hydrophobic barium titanate composite particle, if the hydrophobic particle is the zinc oxide particle, the hydrophobic particle covered by the dopamine layer forms a hydrophobic zinc oxide composite particle, the hydrophobic barium titanate composite particle or the hydrophobic zinc oxide composite particle covers the hydrophobic LLZO particle, and forming the composite LLZO particle, Step C includes reducing the rotational speed of the wet mixer to a third rotational speed, i.e., the third rotational speed being slower than the second rotational speed in step B. Each of the composite LLZO particles formed in step C comprises a first LLZO particle for guiding and dispersing lithium ions passing through the electrode, the outer surface of the first LLZO particle is coated with a corresponding hydroxide ion layer, and the outside of the hydroxide ion layer is coated with a corresponding dopamine layer to form the hydrophobic LLZO particle, the dopamine molecules in the dopamine layer are hydrophobic and therefore further protect the first LLZO particle, the outer hydrophobic layer coats the outer surface of the hydrophobic LLZO particle to form the composite LLZO particle, the outer hydrophobic layer is formed by a plurality of corresponding hydrophobic barium titanate composite particles, a plurality of corresponding hydrophobic zinc oxide composite particles, or a combination thereof. A method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer, characterized in that the outer surface of each barium titanate particle in the hydrophobic barium titanate composite particles and the outer surface of each zinc oxide particle in the hydrophobic zinc oxide composite particles are each coated with a corresponding hydroxide ion layer, and the outer surface of the hydroxide ion layer of the barium titanate particles and the zinc oxide particles is coated with a corresponding dopamine layer, and the dopamine molecules of the dopamine layer of the hydrophobic LLZO particles and the dopamine molecules of the dopamine layer of the outer hydrophobic layer undergo a chain copolymerization reaction so that the outer hydrophobic layer coats the outer surface of the hydrophobic LLZO particles.

2. The method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer, as described in claim 1, further comprising step D, in step C, in which the third mixed slurry is introduced into a rotary evaporator to remove most methanol and other unwanted residues, and then dried to evaporate the methanol, hydrochloric acid, and other solvents from the third mixed slurry to obtain a final powder.

3. A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 1 or 2, characterized in that, in step C, the third mixed slurry is formed, and then an alcohol-based solution containing a plurality of carbon nanotubes (CNTs) is introduced into the wet mixer and mixed and stirred with the third mixed slurry, thereby coating the outer surface of each of the composite LLZO particles with a plurality of corresponding carbon nanotubes to form composite LLZO particles that coat a carbon material.

4. The method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 3, further comprising a plurality of nanoscale amorphous carbons in the alcohol-based solution, wherein the size of each of the nanoscale amorphous carbons is in the range of 10 nm to 40 nm.

5. A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 3, characterized in that the length of the carbon nanotubes is in the range of 0.5 μm to 3 μm.

6. The weight ratio of the total weight of the multiple first LLZO particles to the methanol is in the range of 0.8 to 1.2:

4. The weight ratio of the total weight of the multiple hydrophobic particles to the total weight of the multiple first LLZO particles is in the range of 1 / 25 to 1 / 10. The method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 3, characterized in that the weight ratio of the alcohol-based solution to the third mixed slurry is in the range of 0.01 to 0.5:

100.

7. A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 1, characterized in that a plurality of the composite LLZO particles are used as the negative electrode of a solid or semi-solid battery.

8. Each of the first LLZO particles is lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer according to claim 1, characterized in that the particles are formed of lithium lanthanum zirconium oxide doped with LLZO or at least one metal element.

9. A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 2, characterized in that, after going through step D, the size of each composite LLZO particle is in the range of 50 nm to 200 nm and exhibits an irregular three-dimensional shape.

10. In step B, the weight ratio of the tris(hydroxymethyl)aminomethane to the tris(hydroxymethyl)aminomethane hydrochloride is 8:

2. A method for producing composite ceramic electrolyte particles for battery electrodes that coat a hydrophobic protective layer, as described in claim 1, characterized in that, in step C, the weight ratio of the total weight of the plurality of first LLZO particles, the total weight of the tris(hydroxymethyl)aminomethane and the tris(hydroxymethyl)aminomethane hydrochloride, and the weight of the dopamine hydrochloride is in the range of 1:0.8 to 1:2.2 to 2.

4.

11. A method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that, in step C, the thickness of the dopamine layer is in the range of 1 nm to 10 nm.

12. In step A, the first rotational speed of the wet mixer is 2200 rpm ± 20%, the particle size of the zirconium beads is in the range of 0.7 mm to 0.9 mm, the filling rate of the total volume of the zirconium beads is in the range of 70% to 90%, the polishing time is in the range of 1 hour to 1.5 hours, and the operating temperature is 20°C ± 4°C. In step B, the second rotational speed of the wet mixer is 2400 rpm ± 20%, the polishing time is 0.5 hours, and the operating temperature is 20°C ± 4°C. A method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer, as described in claim 1, characterized in that, in step C, the third rotational speed of the wet mixer is 2000 rpm ± 20%, the polishing time is in the range of 0.5 hours to 1 hour, and the operating temperature is 20°C ± 4°C.

13. A method for producing composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer, as described in claim 3, characterized in that, in step C, the alcohol-based solution is added, and then the wet mixer is continuously polished at a rotational speed of 2000 rpm ± 20% for 0.5 hours, and the operating temperature is 20 ± 4°C.

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