Composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer

Abstract

The present invention provides composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer. [Solution] The composite LLZO particle 100 comprises a first LLZO particle, a first hydroxide ion layer covering the outer surface of the first LLZO particle and forming a secondary LLZO composite particle as a whole, a first dopamine layer covering the outside of the secondary LLZO composite particle and forming a hydrophobic LLZO particle 40, and an outer hydrophobic layer 41 covering the outer surface of the hydrophobic LLZO particle and forming a composite LLZO particle. The outer hydrophobic layer contains a plurality of peripheral composite particles formed by a plurality of barium titanate composite particles 20 or a plurality of zinc oxide composite particles 22, or a combination of both. Each of the peripheral composite particles contains a peripheral particle, and the outer surface of the peripheral particle is covered by a second hydroxide ion layer.

Description

[Technical Field]

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

[0002] A battery is formed primarily by placing a positive electrode and a negative electrode in an electrolyte. In conventional technology, the ionic conductivity is increased by adding LLZO (lithium lanthanum zirconium oxide) 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 guide them, dispersing the lithium ion pathway. This ensures that lithium ions are distributed uniformly in channels within the negative electrode, preventing abnormal accumulation of lithium ions in the negative electrode slurry and causing 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 since the LLZO material is hydrophilic, the LLZO material readily reacts with water, becoming wet and generating alkaline substances, which degrades the material of the negative electrode slurry.

[0004] Therefore, the inventors believed that the above-mentioned drawbacks could be improved, and after diligent research, they arrived at the proposal of composite ceramic electrolyte particles for battery electrodes coated with the hydrophobic protective layer of the present invention, which effectively improves the above-mentioned problems through a rational design.

[0005] This invention has been made in view of these circumstances, and its objective is to provide composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer. [Means for solving the problem]

[0006] To solve the above problems, the composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to an aspect of the present invention are composite LLZO particles, and the composite LLZO particles are used for electrodes of solid or semi-solid batteries. The electrode includes an electrode substrate and an electrode slurry layer coated on the electrode substrate. The composite LLZO particles are used to guide and disperse lithium ions that have passed through the electrode, and can form a uniformly distributed lithium ion channel in the electrode. The composite LLZO particles include first LLZO particles, a first hydroxide ion layer covering the outer surface of the first LLZO particles. The first hydroxide ion layer and the first LLZO particles form secondary LLZO composite particles. The first hydroxide ion layer is formed by adding tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2) and reacting it in the process of the composite LLZO particles. Tris(hydroxymethyl)aminomethane has three OH - ions, namely first OH - ions, second OH - ions, and third OH - ions. The first OH - ions and the second OH - ions form hydrogen bonds with oxidation functional groups on the first LLZO particles, and the third OH - ions extend outward from the first LLZO particles to form the first hydroxide ion layer that forms the first hydroxide ion layer, a first dopamine layer covering the outside of the secondary LLZO composite particles. The first dopamine layer and the secondary LLZO composite particles form hydrophobic LLZO particles. The first dopamine layer is formed by a copolymerization reaction between a plurality of dopamine molecules. Each OH - ion of the dopamine molecules in the first dopamine layer is the third OH of the first hydroxide ion layer -A dehydration polymerization reaction with ions is generated to bind the first dopamine layer to the secondary LLZO composite particles, and the dopamine molecules in the first dopamine layer are hydrophobic and are used to protect the first LLZO particles from getting wet. An outer hydrophobic layer covering the outer surface of the hydrophobic LLZO particles, wherein the outer hydrophobic layer and the hydrophobic LLZO particles form the composite LLZO particles, the outer hydrophobic layer includes a plurality of peripheral composite particles, and the plurality of peripheral composite particles are formed by a plurality of barium titanate composite particles or a plurality of zinc oxide composite particles, or a combination thereof, comprising the outer hydrophobic layer, Each of the surrounding composite particles includes surrounding particles, and if the surrounding composite particle is the barium titanate composite particle, the surrounding particle is a barium titanate particle; if the surrounding composite particle is the zinc oxide composite particle, the surrounding particle is a zinc oxide particle; the outer surface of the surrounding particle is covered with a second hydroxide ion layer; and the outer surface of the second hydroxide ion layer is covered with a second dopamine layer. The second hydroxide ion layer is formed by adding and reacting tris(hydroxymethyl)aminomethane in the composite LLZO particle process, and the tris(hydroxymethyl)aminomethane is the first OH - Ions and second OH - Ions and 3OH - The three OH groups of ions - Having an ion, the first OH - Ions and the aforementioned 2OH - The ions form hydrogen bonds with the oxidative functional groups in the corresponding barium titanate particles or zinc oxide particles, and the 3OH - The ions extend outward from the barium titanate particles or the zinc oxide particles to form the second hydroxide ion layer, and each of the second dopamine layers of the surrounding composite particles is formed by copolymerization reactions between multiple dopamine molecules, and each of the OH- ions of the dopamine molecules in the second dopamine layer corresponds to the third OH in the corresponding second hydroxide ion layer. -Generate a dehydration polymerization reaction with ions (polymerization triggered by dehydration) to bond the second dopamine layer to the corresponding barium titanate particles or the zinc oxide particles, The dopamine molecules in the first dopamine layer and the dopamine molecules in the second dopamine layer of the outer hydrophobic layer undergo a chain copolymerization reaction, and the outer hydrophobic layer covers the outer surface of the hydrophobic LLZO particles.

Advantages of the Invention

[0007] Thus, according to the present invention, the following effects are achieved. By coating the outer surface of the first LLZO particles with a dopamine layer, hydrophobic LLZO particles are formed, and by coating the outside of the hydrophobic LLZO particles with barium titanate composite particles or zinc oxide composite particles having a dopamine layer, suitable ion conduction is formed. Since the dopamine layer has hydrophobicity, it becomes difficult for moisture to further enter the first LLZO particles, and since the barium titanate composite particles or zinc oxide composite particles also have hydrophobicity, further protection for the first LLZO particles is formed. The present invention further adds carbon nanotubes and nanoscale amorphous carbon as conductive agents. By filling the gaps between the carbon nanotubes with the nanoscale amorphous carbon, the conductivity is enhanced. The present invention forms multiple layers of protection by the barium titanate composite particles or zinc oxide composite particles, the dopamine layer, the carbon nanotubes, and the nanoscale amorphous carbon, so that the entire composite LLZO particle structure has enhanced lithium ion guiding ability, prevents the situation of reacting with water during the manufacturing process of the electrode, and further achieves a suitable manufacturing quality of the battery electrode material.

[0008] Other features of the present invention will be clarified by the description in this specification and the accompanying drawings.

Brief Description of the Drawings

[0009] [Figure 1]It is a schematic configuration diagram showing composite ceramic electrolyte particles for a battery electrode coated with a hydrophobic protective layer according to an embodiment of the present invention. [Figure 2] An example of composite ceramic electrolyte particles for a battery electrode coated with a hydrophobic protective layer according to an embodiment of the present invention is shown. [Figure 3] It is a schematic diagram showing the configuration of secondary LLZO composite particles according to an embodiment of the present invention and a part thereof. [Figure 4] It is a schematic diagram showing the configuration of hydrophobic LLZO particles according to an embodiment of the present invention and a part thereof, and a dehydration copolymerization reaction is formed by OH-ions of dopamine molecules and the third OH-ion of the hydroxide ion layer. [Figure 5] It is a schematic diagram showing the configuration of barium titanate composite particles according to an embodiment of the present invention and a part thereof. [Figure 6] It is a schematic diagram showing the configuration of zinc oxide composite particles according to an embodiment of the present invention and a part thereof. [Figure 7] It is a schematic diagram showing tertiary LLZO composite particles according to an embodiment of the present invention. [Figure 8] It is a schematic cross-sectional view showing composite LLZO particles according to an embodiment of the present invention. [Figure 9] It is a schematic cross-sectional view showing a partial configuration of composite LLZO particles according to an embodiment of the present invention.

Mode for Carrying Out the Invention

[0010] 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 range, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0011] Next, referring to FIGS. 1 to 9, composite ceramic electrolyte particles for a battery electrode coated with a hydrophobic protective layer according to the present invention will be described. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to the present invention are composite LLZO particles 100, which are mainly used in electrodes 10 of solid or semi-solid batteries. When applied, a plurality of composite LLZO particles 100 are arranged within the electrode 10, and the electrode 10 is particularly the negative electrode of the solid or semi-solid battery. The particle size of the composite LLZO particles 100 is in the range of 50 nm to 200 nm. The electrode 10 comprises an electrode substrate 11, which is a substrate on which the material of the electrode 10 is placed, and an electrode slurry layer 13 coated on the electrode substrate 11, wherein the electrode slurry layer 13 contains an electrode slurry 12 as a binder, and the electrode slurry 12 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 manufacture of the electrode slurry 12 is water. The composite LLZO particles 100 are used to guide lithium ions. The weight percentage of the composite LLZO particles 100 in the electrode slurry layer 13 is in the range of 0.5 wt% to 5 wt%.

[0012] The configuration of the composite LLZO particles 100 of the present invention will be described in detail below. The composite LLZO particles 100 mainly have the following configuration. Each of these configurations will be described below.

[0013] First, regarding the first LLZO particles 15, the LLZO material has high ionic conductivity for lithium ions. Therefore, when lithium ions pass through the electrode, the first LLZO particles 15 are used to guide and disperse the lithium ions, enabling the formation of uniformly distributed lithium ion channels within the electrode, and preventing abnormal accumulation of lithium ions in the electrode slurry and causing side reactions with the electrode slurry.

[0014] During the manufacturing process of the electrode, moisture is present, and because the first LLZO particles 15 are hydrophilic, they are prone to chemical reactions when wet, generating alkaline substances. Therefore, the outer layer of the first LLZO particles 15 is covered with a protective layer (dopamine layer 35 below) to prevent the first LLZO particles 15 from getting wet during the manufacturing process of the electrode.

[0015] The first LLZO particle 15 is lithium lanthanum zirconium oxide (Li7La3Zr2O 12 Formed of lithium lanthanum zirconium oxide doped with at least one metallic element (e.g., Li6.2Ga) or LLZO. 0.8 La3Zr2O 12 (Lithium lanthanum zirconate compounds doped with gallium (Ga), or lithium lanthanum zirconate compounds doped with aluminum (Al) or barium (Ba)).

[0016] Next is the first hydroxide ion (OH) - The first hydroxide ion layer 24 covers the outer surface of the first LLZO particles 15, and the first hydroxide ion layer 24 and the first LLZO particles 15 form secondary LLZO composite particles 30 (see Figure 3). The thickness of the first hydroxide ion layer 24 is in the range of 0.5 nm to 2 nm. The first hydroxide ion layer 24 is formed by adding and reacting tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2) in the process of the composite LLZO particles 100, and the tris(hydroxymethyl)aminomethane is the first OH - Ion, 2OH - Ions, and 3OH - Three OH ions - It contains ions. The first OH - Ions and the aforementioned 2OH - The ions form hydrogen bonds with the oxidative functional groups on the first LLZO particles 15, and the third OH -The ions extend outward from the first LLZO particles 15, forming the first hydroxide ion layer 24. The hydroxide ion layer 24 is composed of a corresponding number of the third OH - It contains ions. Figure 3 shows only two tris(hydroxymethyl)aminomethane molecules for illustrative purposes, but this does not limit the scope of the present invention.

[0017] Next, the first dopamine layer 35 coats the outside of the secondary LLZO composite particles 30, and the first dopamine layer 35 and the secondary LLZO composite particles 30 form hydrophobic LLZO particles 40 (see Figure 4). The first dopamine layer 35 is formed by a copolymerization reaction between multiple dopamine molecules. Each of the OH groups of the dopamine molecules in the first dopamine layer 35 - The ions are located in the first hydroxide ion layer 24, the third OH - The first dopamine layer 35 is bonded to the secondary LLZO composite particles 30 by inducing a dehydration polymerization reaction with ions. The thickness of the first dopamine layer 35 is in the range of 1 nm to 10 nm.

[0018] The purpose of coating the outer layer of the secondary LLZO composite particles 30 with the first dopamine layer 35 is mainly because moisture is present during the manufacturing process of the electrode slurry, and since the first LLZO particles 15 are hydrophilic, they generate alkaline byproducts when wet, which destroys their lithium ion guiding properties. However, dopamine is hydrophobic, and by coating the outer surface of the secondary LLZO composite particles 30 with the first dopamine layer 35, the first LLZO particles 15 are further protected from getting wet.

[0019] Next, the outer hydrophobic layer 41 covers the outer surface of the hydrophobic LLZO particles 40, and the outer hydrophobic layer 41 and the hydrophobic LLZO particles 40 form the composite LLZO particles 100 (see Figure 1). The outer hydrophobic layer 41 comprises a plurality of peripheral composite particles 200, and the plurality of peripheral composite particles 200 are formed from a plurality of barium titanate (BaTiO3) composite particles 20 or a plurality of zinc oxide (ZnO) composite particles 22, or a combination of both. The arrangement of the plurality of peripheral composite particles 200 on the outer surface of the hydrophobic LLZO particles 40 is formed naturally during stirring in the process.

[0020] As shown in Figures 5 and 6, each of the surrounding composite particles 200 comprises surrounding particles 210. When the surrounding composite particle 200 is the barium titanate composite particle 20, the surrounding particle 210 is the barium titanate particle 201. When the surrounding composite particle 200 is the zinc oxide composite particle 22, the surrounding particle 210 is the zinc oxide particle 221. The outer surface of the surrounding particle 210 is composed of hydroxyl ions (OH). - The second hydroxide ion layer 21 is covered by a second dopamine layer 36. The particle sizes of the barium titanate composite particles 20 and the zinc oxide composite particles 22 are in the range of 10 nm to 20 nm.

[0021] As shown in Figures 5 and 6, the second hydroxide ion layer 21 is formed by adding and reacting tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2) in the process of the composite LLZO particles 100, and the tris(hydroxymethyl)aminomethane is the first OH - Ion, 2OH - Ions, and 3OH - The three OH groups of ions - It contains ions. The first OH - Ions and the aforementioned 2OH - The ions form hydrogen bonds with the oxidative functional groups in the corresponding barium titanate particles 201 or zinc oxide particles 221.- The ions extend outward from the barium titanate particles 201 or the zinc oxide particles 221, forming the second hydroxide ion layer 21. Each of the second dopamine layers 36 of the peripheral composite particles 200 is formed by copolymerization reactions between multiple dopamine molecules, and each of the OH groups of the dopamine molecules in the second dopamine layer 36 - The ions are located in the corresponding second hydroxide ion layer 21, the third OH - A dehydration polymerization reaction with ions (polymerization triggered by dehydration) is induced to bond the second dopamine layer 36 to the corresponding barium titanate particles 201 or zinc oxide particles 221. Figures 5 and 6 show only two tris(hydroxymethyl)aminomethane molecules for illustrative purposes, but this does not limit the scope of the present invention.

[0022] The weight ratio of the outer hydrophobic layer 41 to the weight of the hydrophobic LLZO particles 40 is in the range of 1 / 25 to 1 / 10 (4% to 10%). The thickness of the second hydroxide ion layer 21 is in the range of 0.5 nm to 2 nm. The thickness of the second dopamine layer 36 is in the range of 1 nm to 10 nm.

[0023] As the outer hydrophobic layer 41 coats the outer surface of the hydrophobic LLZO particles 40, a chain copolymerization reaction occurs between the dopamine molecules of the first dopamine layer 35 and the dopamine molecules of the second dopamine layer 36 in the outer hydrophobic layer 41, causing the outer hydrophobic layer 41 to coat the outer surface of the hydrophobic LLZO particles 40. This bond is a structure that is naturally formed during stirring in the process.

[0024] The purpose of coating with the outer hydrophobic layer 41 is to further isolate moisture from the hydrophobic LLZO particles 40 so that the hydrophobic LLZO particles 40 do not get wet when the barium titanate composite particles 20 or the zinc oxide composite particles 22 coat the outer surface of the hydrophobic LLZO particles 40, since the barium titanate particles 201 and the zinc oxide particles 221 themselves are hydrophobic. In addition, since the ionic conductivity of the barium titanate particles 201 is superior to that of the first LLZO particles 15, it is possible to form a suitable ionic conductivity overall. The zinc oxide particles 221 improve electrode compatibility and the ionic boundary layer and have the function of an electrode material, so the capacitance that decreases and is lost by coating can be suppressed.

[0025] The purpose of covering the outer surface of the peripheral particles 210 with the second hydroxide ion layer 21 is that the barium titanate particles 201 and the zinc oxide particles 221 are insoluble in water, and hydroxide ions (OH) are present. - Because the ions are polar, the outside of the barium titanate particles 201 and the zinc oxide particles 221 are coated with the second hydroxide ion layer 21, which reacts with the dopamine molecules of the corresponding second dopamine layer 36, causing the second dopamine layer 36 to adhere more stably to the barium titanate particles 201 or the zinc oxide particles 221.

[0026] The present invention further comprises a plurality of carbon nanotubes 42 (CNTs) and a plurality of nanoscale amorphous carbon 45, which coat the outer surface of the composite LLZO particles 100 to form tertiary LLZO composite particles 50 (see Figure 7). The size of the carbon nanotubes 42 is in the range of 200 nm to 500 nm, and the size of the nanoscale amorphous carbon 45 is in the range of 10 nm to 40 nm. The nanoscale amorphous carbon 45 is, for example, an amorphous carbon of a super P conductive agent.

[0027] In the tertiary LLZO composite particles 50, the weight ratio of the total weight of the multiple carbon nanotubes 42 and the multiple nanoscale amorphous carbon 45 to the weight of the first LLZO particles 15 is in the range of 0.2 to 2 and 99.8 to 98.

[0028] Both the nanoscale amorphous carbon 45 and the carbon nanotubes 42 are used as conductive agents. The nanoscale amorphous carbon 45 exhibits a particle form, and the carbon nanotubes 42 exhibit an elongated form. Gaps are formed between multiple carbon nanotubes 42 that intersect vertically and horizontally, and current cannot be conducted in these gaps. When multiple nanoscale amorphous carbon 45 fill the gaps, the charge is conducted to the next carbon nanotube 42 by the nanoscale amorphous carbon 45 straddling each other, further increasing the transmission of current. When multiple carbon nanotubes 42 adhere to the composite LLZO particles 100, a ball-like structure is formed (see Figure 7).

[0029] An advantage of the carbon nanotube 42 is that lithium ions are easily stabilized between the carbon nanotubes 42, resulting in a large number of lithium ions becoming firmly fixed and increasing the overall conductivity of the lithium ions. Furthermore, electrons can be easily fixed between multiple carbon nanotubes 42, further increasing the overall conductivity of the lithium ions. In addition, the very high conductivity of the ions facilitates fast charging and discharging of the entire battery, further reducing the amount of cobalt used and lowering the overall production cost.

[0030] An advantage of the present invention is that hydrophobic LLZO particles are formed by coating the outer surface of the first LLZO particles with a dopamine layer, and the outside of the hydrophobic LLZO particles is coated with barium titanate composite particles or zinc oxide composite particles having a dopamine layer, thereby forming suitable ionic conductivity. Because the dopamine layer is hydrophobic, moisture is less likely to penetrate further into the first LLZO particles. The barium titanate composite particles or zinc oxide composite particles are also hydrophobic, thus providing further protection to the first LLZO particles. The present invention further adds carbon nanotubes and nanoscale amorphous carbon as conductive agents. The nanoscale amorphous carbon fills the gaps between the carbon nanotubes, enhancing the conductivity. The present invention enhances the lithium ion guiding ability of the entire composite LLZO particle structure by forming a multilayer protection with the barium titanate composite particles or zinc oxide composite particles, the dopamine layer, the carbon nanotubes, and the nanoscale amorphous carbon, and also prevents reactions with water during the electrode manufacturing process, thereby achieving a more suitable manufacturing quality for battery electrode materials.

[0031] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit its interpretation. The present invention may be modified and improved without departing from its spirit, and it goes without saying that equivalents thereof are included. [Explanation of Symbols]

[0032] 10 electrodes 11 Electrode substrate 12 Electrode slurry 13 Electrode slurry layer 15. First LLZO particle 20 Barium titanate composite particles 21 Second hydroxide ion layer 22 Zinc oxide composite particles 24. First hydroxide ion layer 30 Secondary LLZO composite particles 35. Dopamine Layer 1 36. Second Dopamine Layer 40 Hydrophobic LLZO particles 41 Outer hydrophobic layer 42 Carbon nanotubes 45 nanoscale amorphous carbon 50 Tertiary LLZO composite particles 100 composite LLZO particles 200 surrounding composite particles 201 Barium titanate particles 210 surrounding particles 221 Zinc Oxide Particles

Claims

1. A composite ceramic electrolyte particle for battery electrodes coated with a hydrophobic protective layer which is a composite LLZO particle, wherein the composite LLZO particle is used as an electrode for a solid or semi-solid battery, and the electrode comprises an electrode substrate and an electrode slurry layer coated on the electrode substrate, and the composite LLZO particle is A first LLZO particle is used to guide and disperse lithium ions that have passed through the electrode, and the electrode contains a first LLZO particle capable of forming uniformly distributed lithium ion channels. A first hydroxide ion layer covering the outer surface of the first LLZO particles, wherein the first hydroxide ion layer and the first LLZO particles form secondary LLZO composite particles, and the first hydroxide ion layer is formed by adding and reacting tris(hydroxymethyl)aminomethane (tris(hydroxymethyl)aminomethane, (HOCH 2 )) 3 CNH 2 ) in the process of the composite LLZO particles. 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 form hydrogen bonds with oxidation functional groups on the first LLZO particles, and the third OH - ion extends outward from the first LLZO particles to form the first hydroxide ion layer, which is the first hydroxide ion layer that forms the first hydroxide ion layer A first dopamine layer coating the outside of the secondary LLZO composite particles, wherein the first dopamine layer and the secondary LLZO composite particles form hydrophobic LLZO particles, the first dopamine layer is formed by a copolymerization reaction between a plurality of dopamine molecules, and each of the OH groups of the dopamine molecules in the first dopamine layer - The ions are the third OH in the first hydroxide ion layer. - A dehydration polymerization reaction with ions is generated to bind the first dopamine layer to the secondary LLZO composite particles, and the dopamine molecules in the first dopamine layer are hydrophobic and are used to protect the first LLZO particles from getting wet. An outer hydrophobic layer covering the outer surface of the hydrophobic LLZO particles, wherein the outer hydrophobic layer and the hydrophobic LLZO particles form the composite LLZO particles, the outer hydrophobic layer includes a plurality of peripheral composite particles, and the plurality of peripheral composite particles are formed by a plurality of barium titanate composite particles or a plurality of zinc oxide composite particles, or a combination thereof, comprising the outer hydrophobic layer, Each of the surrounding composite particles includes surrounding particles, and if the surrounding composite particle is the barium titanate composite particle, the surrounding particle is a barium titanate particle; if the surrounding composite particle is the zinc oxide composite particle, the surrounding particle is a zinc oxide particle; the outer surface of the surrounding particle is covered with a second hydroxide ion layer; and the outer surface of the second hydroxide ion layer is covered with a second dopamine layer. The second hydroxide ion layer is formed by adding and reacting tris(hydroxymethyl)aminomethane in the composite LLZO particle process, and the tris(hydroxymethyl)aminomethane is the first OH - Ion, 2nd OH - Ions, and 3OH - The three OH groups of ions - Having an ion, the first OH - Ions and the aforementioned second OH - The ions form hydrogen bonds with the oxidative functional groups in the corresponding barium titanate particles or zinc oxide particles, and the 3OH - The ions extend outward from the barium titanate particles or the zinc oxide particles to form the second hydroxide ion layer, and each of the second dopamine layers of the surrounding composite particles is formed by copolymerization reactions between multiple dopamine molecules, and each of the OH groups of the dopamine molecules in the second dopamine layer - The ions are located in the corresponding second hydroxide ion layer, the third OH - A dehydration polymerization reaction (polymerization triggered by dehydration) is generated with ions to bond the second dopamine layer to the corresponding barium titanate particles or zinc oxide particles. A composite ceramic electrolyte particle for a battery electrode, coated with a hydrophobic protective layer, characterized in that the dopamine molecules in the first dopamine layer and the dopamine molecules in the second dopamine layer of the outer hydrophobic layer undergo a chain copolymerization reaction, and the outer hydrophobic layer coats the outer surface of the hydrophobic LLZO particle.

2. The first LLZO particle is lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 Composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that they are formed of lithium lanthanum zirconium oxide doped with LLZO or at least one metal element.

3. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that the weight ratio of the total weight of the outer hydrophobic layer to the total weight of the hydrophobic LLZO particles is in the range of 1 / 25 to 1 / 10.

4. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that the particle size of the composite LLZO particles is in the range of 50 nm to 200 nm.

5. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that the particle size of the barium titanate composite particles or the zinc oxide composite particles is in the range of 10 nm to 20 nm.

6. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that the thickness of the first hydroxide ion layer and the second hydroxide ion layer are each in the range of 0.5 nm to 2 nm.

7. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, characterized in that the thickness of the first dopamine layer and the second dopamine layer are each in the range of 1 nm to 10 nm.

8. Composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 1, further comprising a plurality of carbon nanotubes and a plurality of nanoscale amorphous carbon that coat the outer surface of the composite LLZO particles and form tertiary LLZO composite particles.

9. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 8, characterized in that the size of the carbon nanotubes is in the range of 200 nm to 500 nm, and the size of the nanoscale amorphous carbon is in the range of 10 nm to 40 nm.

10. The composite ceramic electrolyte particles for battery electrodes coated with a hydrophobic protective layer according to claim 8, characterized in that the weight ratio of "the total weight of the plurality of carbon nanotubes and the plurality of nanoscale amorphous carbons" to the weight of the first LLZO particles is in the range of 0.2 to 2:99.8 to 98.

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