Oxide ceramic particles coated with amination functional groups

Abstract

The present invention provides oxide ceramic particles coated with amination functional groups. [Solution] The oxide ceramic particles coated with amination functional groups according to the present invention are composite LLZO particles. The composite LLZO particles include first LLZO particles for guiding and dispersing lithium ions passing through the positive electrode, a hydroxide ion layer covering the outer surface of the first LLZO particles and forming a secondary LLZO composite particle overall, and a dopamine layer covering the outside of the secondary LLZO composite particle, wherein the dopamine layer is hydrophobic and can protect the first LLZO particles from getting wet. A CTAB (cetyltrimethylammonium bromide) layer covers the outside of the dopamine layer, and a portion of the CTAB layer is mixed into the dopamine layer and the hydroxide ion layer.

Description

[Technical Field]

[0001] The present invention relates to electrode materials, and more particularly to oxide ceramic particles coated with amination functional groups. [Background technology]

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

[0003] However, in the conventional electrode technology described above, the LLZO material tends to cause side reactions with the electrode material during the manufacturing process of the electrode, resulting in deterioration of the electrode slurry material.

[0004] Therefore, the inventors believed that the above-mentioned drawbacks could be improved, and after diligent research, they arrived at the proposal of oxide ceramic particles coated with amination functional groups of the present invention, which effectively improve the above-mentioned problems through a rational design.

[0005] The present invention has been made in view of these circumstances, and its object is to provide oxide ceramic particles coated with amination functional groups. [Means for solving the problem]

[0006] To solve the above problems, the oxide ceramic particles coating the aminated functional group according to an aspect of the present invention are composite LLZO particles, and the composite LLZO particles are used for the electrodes of solid or semi-solid batteries. The electrodes include 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 passing through the electrode, and are for forming a lithium ion channel uniformly distributed within the electrode. The composite LLZO particles include first LLZO particles and a hydroxide ion layer covering the outer surface of the first LLZO particles. The hydroxide ion layer and the first LLZO particles form secondary LLZO composite particles. The hydroxide ion layer is formed by reacting tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2). The 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 bind to the oxidation functional groups of the first LLZO particles themselves, and the third OH - ions are extended toward the outer surface of the first LLZO particles to form the hydroxide ion layer. The hydroxide ion layer is a hydroxide ion layer containing a plurality of corresponding third OH - ions and a dopamine layer covering the outside of the secondary LLZO composite particles. The dopamine layer is formed by a copolymerization reaction between a plurality of dopamine molecules. The OH - ions of the dopamine molecules generate a dehydration polymerization reaction with the third OH - ions of the hydroxide ion layer, enabling the dopamine molecules to bind to the secondary LLZO composite particles. The dopamine has hydrophobicity and is used to protect the first LLZO particles from getting wet.

Advantages of the Invention

[0007] The present invention forms secondary LLZO composite particles by coating the outer surface of first LLZO particles with a hydroxide ion layer, and then forming composite LLZO particles by coating the outer surface of the secondary LLZO composite particles with a dopamine layer. Because the dopamine layer is hydrophobic, moisture is less likely to penetrate further into the first LLZO particles. The outside of the composite LLZO particles is further coated with particulate nanoscale amorphous carbon and elongated carbon nanotubes as conductive agents. The conductivity is enhanced by filling the gaps between the carbon nanotubes with the nanoscale amorphous carbon. Because the dopamine layer, CTAB, multiple carbon nanotubes, and nanoscale amorphous carbon form a multilayer protection, the entire composite LLZO particle structure has enhanced lithium ion guiding ability, prevents reaction with the electrode slurry material during the electrode manufacturing process, and achieves a more suitable 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 schematic diagram showing oxide ceramic particles coated with an amination functional group according to one embodiment of the present invention. [Figure 2] An example of oxide ceramic particles coated with an amination functional group according to one embodiment of the present invention is shown. [Figure 3] This is a schematic diagram showing the structure and a portion of the hydroxide ion layer according to one embodiment of the present invention. [Figure 4] This is a schematic diagram showing a tertiary LLZO composite particle according to one embodiment of the present invention. [Figure 5] This is a schematic diagram showing a configuration and a portion thereof in which a dehydration copolymerization reaction is formed by the dopamine OH- ions in the dopamine layer and the third OH- ions in the hydroxide ion layer according to one embodiment of the present invention. [Figure 6]It is a schematic diagram showing a partial structure that generates an attractive force by OH - ions of dopamine of CTBA and OH - ions of the hydroxide ion layer according to an embodiment of the present invention. [Figure 7] It is a cross - sectional view showing a CTAB layer coated outside a dopamine layer according to an embodiment of the present invention.

Mode for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the following embodiments and can take various forms as long as it belongs to the technical scope of the present invention.

[0011] First, referring to FIGS. 1 to 7, the oxide ceramic particles coated with an aminated functional group according to the present invention will be described. The oxide ceramic particles coated with an aminated functional group according to the present invention are composite LLZO particles 100, which are mainly used for the electrode 10 of a solid or semi - solid battery. When applied, a plurality of composite LLZO particles 100 are arranged in the electrode 10, and the electrode 10 is particularly the positive electrode of the solid or semi - solid battery. The particle size of the composite LLZO particles 100 is in the range between 50 nm and 200 nm. The electrode 10 includes an electrode substrate 11 for placing the material of the electrode 10, and an electrode slurry layer 13 coated on the electrode substrate 11. The electrode slurry layer 13 includes an electrode slurry 12 as a binder and an electrode slurry layer 13. The electrode slurry layer 13 further includes a plurality of composite LLZO particles 100. The weight percentage of the plurality of composite LLZO particles 100 in the electrode slurry layer 13 is in the range between 0.5 wt% and 5 wt%.

[0012] Hereinafter, the structure of the composite LLZO particles 100 of the present invention will be specifically described. The composite LLZO particles 100 mainly have the following structure. Hereinafter, each structure will be described.

[0013] First, the first LLZO particles 15 are used to guide and disperse lithium ions as they pass through the electrode, because the LLZO material has high ionic conductivity for lithium ions. This allows for the formation of uniformly distributed lithium ion channels within the electrode, preventing abnormal accumulation of lithium ions in the electrode slurry and thus preventing 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 tend to become wet and generate alkaline substances. Therefore, by covering the outer layer of the first LLZO particles 15 with a protective layer (dopamine layer 35 below) according to the present invention, the first LLZO particles 15 are prevented from becoming 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., Li lanthanum zirconium oxide, LLZO) or Li lanthanum zirconium oxide doped with at least one metallic element. 6.2 Ga 0.8 La3Zr2O 12 (This may be a gallium (Ga)-doped lithium lanthanuzirconate compound, or an aluminum (Al) or barium (Ba)-doped lithium lanthanuzirconate compound.)

[0016] Next is the hydroxide ion (OH - The hydroxide ion layer 24 covers the outer surface of the first LLZO particles 15, and the hydroxide ion layer 24 and the first LLZO particles 15 form secondary LLZO composite particles 30 (see Figure 3). The thickness of the hydroxide ion layer 24 is in the range of 0.5 nm to 2 nm. The hydroxide ion layer 24 is formed by reacting tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), which is added 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 on the first LLZO particles 15, and the third OH - A hydroxide ion layer 24 is formed by extending ions toward the outside of the first LLZO particle 15. 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 dopamine layer 35 coats the outside of the secondary LLZO composite particles 30, and the dopamine layer 35 and the secondary LLZO composite particles 30 form the composite LLZO particles 100 (see Figure 1). The dopamine layer 35 is formed by copolymerization reactions between multiple dopamine molecules. Each of the OH groups of the dopamine molecules - The ions are the third OH of the hydroxide ion layer 24. - A dehydration polymerization reaction (polymerization triggered by dehydration) is induced with ions to bind each of the dopamine molecules to the secondary LLZO composite particles 30 (see Figure 5). The thickness of the dopamine layer 35 is in the range of 1 nm to 10 nm.

[0018] The main purpose of coating the outer layer of the secondary LLZO composite particles 30 with the dopamine layer 35 is that moisture is present during the manufacturing process of the electrode slurry, and because the first LLZO particles 15 are hydrophilic, they tend to get wet and generate alkaline byproducts, which destroys their lithium ion guiding properties. Dopamine is hydrophobic, and coating the outer surface of the secondary LLZO composite particles 30 with the dopamine layer 35 further protects the first LLZO particles 15 from getting wet.

[0019] The purpose of coating the outer surface of the first LLZO particles 15 with the hydroxide ion layer 24 is to provide hydroxide ions (OH - Because the hydroxide ion layer 24 has polarity, the dopamine layer 35 is reacted with the dopamine molecules of the dopamine layer 35, thereby further stably attaching the dopamine layer 35 to the secondary LLZO composite particles 30.

[0020] Next, the CTAB (cetyltrimethylammonium bromide) layer 61 covers the outside of the dopamine layer 35 (see Figures 6 and 7). The CTAB layer 61 is composed of multiple CTAB 60. The CTAB is used as a surfactant. A portion of the multiple CTAB 60 is mixed within the dopamine layer 35 and the hydroxide ion layer 24.

[0021] The weight ratio of the total weight of the multiple CTABs 60 in the CTAB layer 61 to the total weight of the dopamine in the dopamine layer 35 is in the range of 0.1% to 0.3%.

[0022] The ratio of the CTAB60 located outside the dopamine layer 35 to the CTAB60 located within the dopamine layer 35 and the hydroxide ion layer 24 is a result of natural occurrence during manufacturing. A portion of the multiple CTAB60 is mixed within the dopamine layer 35 and the hydroxide ion layer 24, while the remaining CTAB60 is located on the outer periphery of the dopamine layer 35 (i.e., the CTAB layer 61). Each of the CTAB60 generates an attractive force with molecules of different polarity within the dopamine layer 35 and the hydroxide ion layer 24 due to the polarity of its molecule.

[0023] CTAB further enhances the dispersibility of the first LLZO particles 15, reducing the probability of lithium fluorination (fluorination induced by interaction with Li) between the first LLZO particles 15 and the PVDF (polyvinylidene fluoride) of the positive electrode slurry without causing aggregation. Aggregation is prevented by concentrating the charge of the first LLZO particles 15. During the modification process of the first LLZO particles 15, at least one exposed OH is present on the surface of the first LLZO particles 15. - Ions (the third OH of the hydroxide ion layer 24) - Ions or OH of dopamine molecules in the dopamine layer 35 - There is a possibility that ions (including ions) will be generated, and one side of the CTAB will be positively charged, while the other side will be negatively charged (see Figure 6). The positively charged area of ​​the CTAB is the exposed OH mentioned above. - It can generate an attractive force with ions, improve the integrity of the surface coating of the composite LLZO particles 100 without altering the overall electrical properties, but without agglutinating dopamine, without exposing the composite LLZO particles 100, and without generating alkalinity.

[0024] During the manufacturing process, not necessarily all of the hydroxide ion layer 24 of the third OH - Ions and all dopamine OH - Since the ions do not together cause a dehydration polymerization reaction, the exposed OH - Ions are formed, and the CTAB is exposed OH - It generates an attractive force with ions, forming a layered protective structure, and further enhancing overall coverage.

[0025] 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 4). 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.

[0026] In the tertiary LLZO composite particles 50, the weight ratio of the total weight of the multiple carbon nanotubes 42 and the nanoscale amorphous carbon 45 to the total weight of the first LLZO particles 15 is in the range of 0.2 to 2 and 99.8 to 98.

[0027] Both the nanoscale amorphous carbon 45 and the carbon nanotube 42 are used as conductive agents. The nanoscale amorphous carbon 45 has a particle form, and the carbon nanotube 42 has 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 spanning each other, further increasing the transmission of current.

[0028] The advantages of the carbon nanotube 42 include the fact that lithium ions are easily stabilized between the carbon nanotubes 42, resulting in a large number of lithium ions becoming firmly fixed, increasing the overall conductivity of lithium ions, and electrons can be easily fixed between multiple carbon nanotubes 42, further increasing the overall conductivity of lithium ions. In addition, the very high ion conductivity helps with fast charging and discharging of the entire battery, reduces the amount of cobalt used, and lowers the overall production cost.

[0029] Although the present invention has been described above using embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications or improvements can be made to the above embodiments. It will be clear from the claims that such modified or improved forms may also be included in the technical scope of the present invention. [Explanation of Symbols]

[0030] 10 electrodes 11 Electrode substrate 12 Electrode slurry 13 Electrode slurry layer 15. First LLZO particle 24. Hydroxide ion layer 30 Secondary LLZO composite particles 35 Dopamine layer 42 Carbon nanotubes 45 nanoscale amorphous carbon 50 Tertiary LLZO composite particles 61 CTAB layer 60 CTAB 100 composite LLZO particles

Claims

1. A composite LLZO particle is an oxide ceramic particle coated with an amination functional group, wherein the composite LLZO particle is used as an electrode in 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 passing through the electrode, and to form a lithium ion channel uniformly distributed within the electrode. A hydroxide ion layer covering the outer surface of the first LLZO particles, wherein the hydroxide ion layer and the first LLZO particles form secondary LLZO composite particles, and the hydroxide ion layer is formed by reacting with tris(hydroxymethyl)aminomethane (HOCH - ), 3 CNH 2 ), and the tris(hydroxymethyl)aminomethane has three OH - ions, namely a first OH - ion, a second OH - ion, and a third OH - ion. The first OH - ion and the second OH - ion are bonded to the oxidation functional groups of the first LLZO particles themselves, and the third OH - ion is extended toward the outer surface of the first LLZO particles to form the hydroxide ion layer. The hydroxide ion layer includes a hydroxide ion layer containing a plurality of corresponding third OH - ions, and - ions, and ions, and The dopamine layer coating the outside of the secondary LLZO composite particles is formed by a copolymerization reaction between multiple dopamine molecules, and the OH of the dopamine molecules - The ions are the third OH in the hydroxide ion layer. - Oxide ceramic particles coated with amination functional groups, characterized by comprising: a dopamine layer that generates a dehydration polymerization reaction with ions to enable the dopamine molecules to bind to the secondary LLZO composite particles, the dopamine being hydrophobic, and used to protect the first LLZO particles from becoming wet.

2. The composite LLZO particles further comprise a CTAB (cetyltrimethylammonium bromide) layer coating the outside of the dopamine layer, wherein the CTAB layer is formed by a plurality of CTABs, and the CTABs are surfactants, characterized in that the oxide ceramic particles coating the amination functional group are as described in claim 1.

3. The weight ratio of the total weight of the multiple CTABs in the CTAB layer to the total weight of the dopamine in the dopamine layer is in the range of 0.1% to 0.3%. The oxide ceramic particles coated with an amination functional group according to claim 2, characterized in that the CTAB further enhances the dispersibility of the first LLZO particles and generates aggregation, and reduces the possibility of lithium fluoride formation between the first LLZO particles and the cathode slurry.

4. The oxide ceramic particles coated with an amination functional group according to claim 1, characterized in that the composite LLZO particles are used as a positive electrode.

5. The oxide ceramic particles coated with an amination functional group 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.

6. The oxide ceramic particles coated with an amination functional group according to claim 1, characterized in that the thickness of the hydroxide ion layer is in the range of 0.5 nm to 2 nm.

7. The oxide ceramic particles coated with amination functional groups according to claim 1, characterized in that the thickness of the dopamine layer is in the range of 1 nm to 10 nm.

8. The oxide ceramic particle coating an amination functional group according to claim 1 or 2, further comprising a plurality of carbon nanotubes and a plurality of nanoscale amorphous carbons coating the outer surface of the composite LLZO particle.

9. The oxide ceramic particles coated with amination functional groups 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 oxide ceramic particles coated with amination functional groups according to claim 8, characterized in that the weight ratio of "the total weight of the plurality of carbon nanotubes and the nanoscale amorphous carbon" to the total weight of the first LLZO particles is in the range of 0.2 to 2:99.8 to 98.

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