Oxide ceramic particles coated with aminated functional groups.

Abstract

Oxide ceramic particles coated with aminated functional groups are provided. [Solution] The oxide ceramic particle is a composite LLZO particle 100. The composite LLZO particle includes a first LLZO particle 15 for guiding and dispersing lithium ions passing through the positive electrode, a hydroxide ion layer 24 that covers the outer surface of the first LLZO particle and collectively forms a secondary LLZO composite particle 30, and a dopamine layer 35 that covers the outside of the secondary LLZO composite particle, has hydrophobicity, and can protect the first LLZO particle from getting wet. A CTAB (cetyltrimethylammonium bromide) layer 61 covers the outside of the dopamine layer, and a portion of the CTAB layer is mixed in 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 aminated functional groups. [Background technology]

[0002] Batteries are mainly formed by placing electrodes (positive and negative electrodes) in an electrolyte, and in the conventional technology, ionic conductivity is increased by adding LLZO (lithium lanthanum zirconium oxide) material to the electrodes. Since LLZO material has high ionic conductivity for lithium ions, when lithium ions pass through the electrode, the dispersed LLZO particles guide them to disperse the lithium ion passages, distributing the lithium ions in uniform channels inside the electrode, preventing lithium ions from abnormally accumulating in the electrode slurry and causing side reactions with the electrode slurry. Summary of the Invention [Problem to be solved by the invention]

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

[0004] Therefore, the present inventors believed that the above-mentioned drawbacks could be improved, and after extensive research, they came up with the invention of oxide ceramic particles coated with aminated functional groups, which effectively improves the above-mentioned problems through rational design.

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

[0006] In order to solve the above problems, the oxide ceramic particles coated with an aminated functional group in one embodiment of the present invention are composite LLZO particles, and the composite LLZO particles are used in an electrode of a solid or semi-solid battery, the electrode comprising an electrode substrate and an electrode slurry layer coated on the electrode substrate, and the composite LLZO particles are: first LLZO particles for forming lithium ion channels uniformly distributed within the electrode, which are used to guide and distribute lithium ions through the electrode; a hydroxide ion layer covering an outer surface of the first LLZO particle, the hydroxide ion layer and the first LLZO particle forming a secondary LLZO composite particle, the hydroxide ion layer being formed by reacting tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), the tris(hydroxymethyl)aminomethane being a first OH - ion, secondary OH - ion, and tertiary OH - 3 OH ions - ions, - ion and the secondary OH - The ions bond with the oxidized functional groups of the first LLZO particles themselves, and the third OH - ions toward the outer surface of the first LLZO particle to form the hydroxide ion layer, the hydroxide ion layer being formed by a corresponding plurality of the third OH - a hydroxide ion layer containing ions; a dopamine layer coating the exterior of the secondary LLZO composite particle, the dopamine layer being formed by a copolymerization reaction between a plurality of dopamine molecules, and OH of the dopamine molecules being - The ions are the tertiary OH ions of the hydroxide ion layer. -a dopamine layer that causes a dehydration polymerization reaction with ions to bind the dopamine molecules to the secondary LLZO composite particles, the dopamine being hydrophobic and used to protect the first LLZO particles from getting wet; the composite LLZO particles further include a CTAB (cetyltrimethylammonium bromide) layer that coats the outside of the dopamine layer, the CTAB layer being formed by a plurality of CTABs, the CTAB being a surfactant; A portion of the multiple CTAB molecules are mixed in the dopamine layer and the hydroxide ion layer, and each of the CTAB molecules generates an attractive force with molecules of different polarity in the dopamine layer and the hydroxide ion layer due to the polarity of the molecule. Effect of the Invention

[0007] The present invention provides a method for forming a composite LLZO particle by coating the outer surface of a first LLZO particle with a hydroxide ion layer, and then coating the outer surface of the second LLZO composite particle with a dopamine layer. The dopamine layer is hydrophobic, so that moisture is more difficult to penetrate into the first LLZO particle. The outer surface of the composite LLZO particle is further coated with nanoscale amorphous carbon particles and elongated carbon nanotubes as conductive agents. The nanoscale amorphous carbon is filled in the gaps of the carbon nanotubes to enhance the conductive ability. The dopamine layer, CTAB, a plurality of the carbon nanotubes, and the nanoscale amorphous carbon form a multi-layer protection, so that the entire composite LLZO particle structure has enhanced lithium ion guiding ability, and prevents reaction with the material of the electrode slurry during the electrode manufacturing process, thereby achieving a suitable manufacturing quality of the battery electrode material.

[0008] Other features of the present invention will become apparent from the description of this specification and the accompanying drawings. [Brief description of the drawings]

[0009] [Figure 1] 1 is a schematic diagram showing an oxide ceramic particle coated with an aminated functional group according to an embodiment of the present invention; FIG. [Diagram 2] 1 shows an example of an oxide ceramic particle coated with aminated functional groups according to one embodiment of the present invention. [Diagram 3] 1 is a schematic diagram showing the structure and parts of a hydroxide ion layer according to an embodiment of the present invention; [Figure 4] FIG. 2 is a schematic diagram showing a tertiary LLZO composite particle according to an embodiment of the present invention; [Diagram 5] 2 is a schematic diagram showing a configuration and part of a dehydration copolymerization reaction between the OH- ions of dopamine in the dopamine layer and the third OH- ions of the hydroxide ion layer in accordance with one embodiment of the present invention; FIG. [Figure 6] FIG. 2 is a schematic diagram showing a partial configuration in which an attractive force is generated by the OH- ions of dopamine in the CTBA and the OH- ions of the hydroxide ion layer in one embodiment of the present invention; [Figure 7] FIG. 2 is a cross-sectional view of a CTAB layer coated on the outside of a dopamine layer according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the present invention will be described with reference to the drawings. Note that the present invention is not limited to the following embodiment, and various forms may be adopted as long as they fall within the technical scope of the present invention.

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

[0012] The composition of the composite LLZO particle 100 of the present invention will be specifically described below. The composite LLZO particle 100 mainly comprises the following components. Each component will be described below.

[0013] First, since the first LLZO particles 15 have high ionic conductivity for lithium ions of the LLZO material, the first LLZO particles 15 are used to guide and disperse the lithium ions as they pass through the electrode, making it possible to form lithium ion channels that are uniformly distributed 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 the first LLZO particles 15 are hydrophilic and therefore prone to become wet and produce alkaline substances. Therefore, by covering the outer layer of the first LLZO particles 15 of the present invention with a protective layer (dopamine layer 35 described below), the first LLZO particles 15 are prevented from becoming wet during the manufacturing process of the electrode.

[0015] The first LLZO particles 15 are made of lithium lanthanum zirconium oxide (Li7La3Zr2O 12 , LLZO) or lithium lanthanum zirconium oxide doped with at least one metal element (e.g., Li 6.2 Ga 0.8 La3Zr2O 12 , which may be gallium (Ga) doped lithium lanthanum zirconate, or aluminum (Al) or barium (Ba) doped lithium lanthanum zirconate.

[0016] Next, the hydroxide ion (OH - A hydroxide ion layer 24 covers the outer surface of the first LLZO particle 15, and the hydroxide ion layer 24 and the first LLZO particle 15 form a secondary LLZO composite particle 30 (see FIG. 3). The thickness of the hydroxide ion layer 24 ranges between 0.5 nm and 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 particle 100, and the tris(hydroxymethyl)aminomethane is a primary OH ion. - ion, secondary OH - ion, and tertiary OH - 3 OH ions - The first OH ion is - ion and the secondary OH - The ions form hydrogen bonds with the oxidized functional groups on the first LLZO particles 15, and the third OH - The hydroxide ion layer 24 is formed by extending the ions toward the outside of the first LLZO particle 15. The hydroxide ion layer 24 is formed by extending the ions toward the outside of the first LLZO particle 15. - ions. Only two tris(hydroxymethyl)aminomethane molecules are shown in Figure 3 for illustrative purposes, but this is not intended to limit the scope of the invention.

[0017] Next, a dopamine layer 35 coats the exterior of the secondary LLZO composite particle 30, and the dopamine layer 35 and the secondary LLZO composite particle 30 form the composite LLZO particle 100 (see FIG. 1). The dopamine layer 35 is formed by a copolymerization reaction between multiple dopamine molecules. Each OH of the dopamine molecule is - The ions are the tertiary OH ions of the hydroxide ion layer 24. - A polymerization reaction triggered by dehydration with ions occurs to bind each of the dopamine molecules to the secondary LLZO composite particles 30 (see FIG. 5). The thickness of the dopamine layer 35 ranges between 1 nm and 10 nm.

[0018] The purpose of coating the outer layer of the secondary LLZO composite particles 30 with the dopamine layer 35 is mainly because moisture exists during the preparation process of the electrode slurry, and the first LLZO particles 15 are hydrophilic materials, so they are prone to get wet and generate alkaline by-products, 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 covering the outer surface of the first LLZO particle 15 with the hydroxide ion layer 24 is to release hydroxide ions (OH - ) has polarity, the hydroxide ion layer 24 reacts with the dopamine molecules of the dopamine layer 35, thereby more stably attaching the dopamine layer 35 to the secondary LLZO composite particle 30.

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

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

[0022] The ratio of the CTAB 60 located outside the dopamine layer 35 and the CTAB 60 located in the dopamine layer 35 and the hydroxide ion layer 24 is a result that occurs naturally during manufacturing. A portion of the CTAB 60 is mixed in the dopamine layer 35 and the hydroxide ion layer 24, and the remaining CTAB 60 is located on the outer periphery of the dopamine layer 35 (i.e., the CTAB layer 61). Each of the CTAB 60 generates an attractive force with molecules of different polarity in the dopamine layer 35 and the hydroxide ion layer 24 due to the polarity of the molecule.

[0023] The use of CTAB further increases the dispersibility of the first LLZO particles 15, preventing aggregation and reducing the probability of lithium fluorination (fluorination induced by interaction with Li) occurring between the first LLZO particles 15 and the PVDF (polyvinylidene fluoride) of the positive electrode slurry. Aggregation does not occur 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 group 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 the dopamine molecules of the dopamine layer 35 -ions) may be generated, and one side of the CTAB is positively charged and the other side is negatively charged (see FIG. 6). The positively charged portion of the CTAB is the exposed OH - It can generate an attractive force with ions, without modifying the overall electrical properties, and increase the completeness of the surface coverage of the composite LLZO particles 100, but it does not aggregate dopamine, does not expose the composite LLZO particles 100, and does not generate alkalinity.

[0024] During the manufacturing process, the third OH of the hydroxide ion layer 24 may not necessarily be present in all of the hydroxide ion layers 24. - ions and all dopamine OH - Since the dehydration polymerization reaction does not occur together with the exposed OH - ions are formed, and the CTAB reacts with the exposed OH - An attractive force with ions is generated, forming a fully laminated protective structure, resulting in more complete overall coverage.

[0025] The present invention further includes a plurality of carbon nanotubes 42 (CNTs) and a plurality of nanoscale amorphous carbons 45, which coat the outer surface of the composite LLZO particle 100 to form a tertiary LLZO composite particle 50 (see FIG. 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, amorphous carbon of super P conductive material.

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

[0027] The nanoscale amorphous carbon 45 and the carbon nanotubes 42 are both conductive materials. The nanoscale amorphous carbon 45 has a particle shape, and the carbon nanotubes 42 have an elongated shape. Gaps are formed between the carbon nanotubes 42 that cross vertically and horizontally, and these gaps cannot conduct electric current. When the nanoscale amorphous carbon 45 fills the gaps, and the nanoscale amorphous carbon 45 crosses over each other, electric charges are conducted to the next carbon nanotube 42, further increasing the current transmission.

[0028] The carbon nanotubes 42 have the advantage that lithium ions are easily stabilized between the carbon nanotubes 42, so that a large number of lithium ions are solid, increasing the overall conductivity of the lithium ions, and electrons can be easily fixed between the carbon nanotubes 42, increasing the overall conductivity of the lithium ions. In addition, the extremely high ion conductivity helps to fast charge and discharge the entire battery, reduces the amount of cobalt used, and reduces the overall production cost.

[0029] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means devised in different embodiments are also 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 The 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, an oxide ceramic particle coated with an aminated functional group, the composite LLZO particle being used in an electrode of a solid or semi-solid battery, the electrode comprising an electrode substrate and an electrode slurry layer coated on the electrode substrate, the composite LLZO particle comprising: first LLZO particles for forming lithium ion channels uniformly distributed within the electrode, which are used to guide and distribute lithium ions through the electrode; a hydroxide ion layer coating an outer surface of the first LLZO particle, the hydroxide ion layer and the first LLZO particle forming a secondary LLZO composite particle, the hydroxide ion layer being tris(hydroxymethyl)aminomethane (HOCH 2 ) 3 CNH 2 ) wherein the tris(hydroxymethyl)aminomethane is a first OH - Ion, 2OH - ion, and tertiary OH - 3 OH ions - ions, - ion and the second OH - The ions bond with the oxidized functional groups of the first LLZO particles themselves, and the third OH - ions toward the outer surface of the first LLZO particle to form the hydroxide ion layer, the hydroxide ion layer corresponding to a plurality of the third OH - a hydroxide ion layer containing ions; a dopamine layer coating the exterior of the secondary LLZO composite particle, the dopamine layer being formed by a copolymerization reaction between a plurality of dopamine molecules, and OH of the dopamine molecules being - The ions are the third OH ions of the hydroxide ion layer. - a dopamine layer that causes a dehydration polymerization reaction with ions to bind the dopamine molecules to the secondary LLZO composite particles, the dopamine being hydrophobic and used to protect the first LLZO particles from getting wet; the composite LLZO particles further include a CTAB (cetyltrimethylammonium bromide) layer that coats the outside of the dopamine layer, the CTAB layer being formed by a plurality of CTABs, the CTAB being a surfactant; A ceramic oxide particle coated with an aminated functional group, characterized in that a portion of the CTAB molecules is mixed into the dopamine layer and the hydroxide ion layer, and each of the CTAB molecules generates an attractive force with molecules of different polarity in the dopamine layer and the hydroxide ion layer due to the polarity of the molecule.

2. a weight ratio of the total weight of the CTABs in the CTAB layer to the total weight of the dopamine in the dopamine layer is in the range of between 0.1% and 0.3%; The oxide ceramic particles coated with aminated functional groups as described in claim 1, characterized in that the CTAB further increases the dispersibility of the first LLZO particles to generate an agglomeration effect, and reduces the possibility of lithium fluoridation occurring between the first LLZO particles and the positive electrode slurry.

3. The oxide ceramic particles coated with aminated functional groups according to claim 1, characterized in that the composite LLZO particles are used in a positive electrode.

4. The oxide ceramic particles coated with aminated functional groups as described in claim 1, characterized in that the particle size of the composite LLZO particles ranges between 50 nm and 200 nm.

5. The oxide ceramic particles coated with aminated functional groups as claimed in claim 1, characterized in that the thickness of the hydroxide ion layer ranges between 0.5 nm and 2 nm.

6. The aminated functional group coated oxide ceramic particles according to claim 1, characterized in that the thickness of the dopamine layer ranges between 1 nm and 10 nm.

7. The oxide ceramic particle coated with an aminated functional group as described in claim 1, further comprising a plurality of carbon nanotubes and a plurality of nanoscale amorphous carbons coating the outer surface of the composite LLZO particle.

8. The oxide ceramic particles coated with aminated functional groups as described in claim 7, characterized in that the size of the carbon nanotubes ranges between 200 nm and 500 nm, and the size of the nanoscale amorphous carbon ranges between 10 nm and 40 nm.

9. The oxide ceramic particles coated with aminated functional groups as described in claim 7, 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 0.2-2:99.8-98.

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