Oxide ceramic particles coated with aminated functional groups

Abstract

The present invention discloses an oxide ceramic particle coated with aminated functional groups, in which the particle is a plurality of composite LLZO particles, the composite LLZO particles comprising: an LLZO particle for directing and dispersing lithium ions passing through the positive electrode; the hydroxide ion layer is coated on the outer surface of the LLZO particle, so as to integrally form a secondary LLZO particle; a dopamine layer is coated outside the secondary LLZO particle, so that the composite LLZO particle is formed; the dopamine has a hydrophobic property, and can further protect the LLZO particles from being affected with damp. CTAB (Cetyltrimethyl Ammonium Bromide) is mixed in the dopamine layer and the hydroxide ion layer, and a CTAB layer is coated outside the dopamine layer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrode materials, and particularly relates to oxide ceramic particles coated with aminated functional groups. BACKGROUND

[0002] A battery is mainly formed by electrodes (anode and cathode) placed in an electrolyte. In the prior art, LLZO material is added to the electrodes to increase ion conductivity. Because the ion conductivity of LLZO material for lithium ions is high, when lithium ions pass through the electrode, the passage of lithium ions can be guided by the dispersed LLZO particles, so that lithium ions can present a uniform channel distribution inside the electrode, avoiding abnormal accumulation of lithium ions in the electrode slurry and causing side reactions with the electrode slurry.

[0003] However, during the manufacturing process of the electrode, the LLZO material is prone to cause side reactions with the materials in the electrode, resulting in degradation of the materials in the electrode slurry. SUMMARY

[0004] The present application solves the technical problem of providing oxide ceramic particles coated with aminated functional groups to solve the above-mentioned defects in the prior art.

[0005] The technical solution of the present application is as follows: providing oxide ceramic particles coated with aminated functional groups, which are coated with a dopamine layer on the outer surface of the secondary LLZO particles. Dopamine has hydrophobic properties, so coating the dopamine layer on the outer surface of the secondary LLZO particles makes it more difficult for moisture to enter the LLZO particles. The present application further coats the nanoscale amorphous carbon and carbon nanotubes as conductive agents on the outer surface of the composite LLZO particles. The nanoscale amorphous carbon is in the form of particles, and the carbon nanotubes are in the form of long strips. The addition of nanoscale amorphous carbon in the voids helps to improve the conductivity of the entire structure. In the present application, the dopamine layer and the plurality of carbon nanotubes and nanoscale amorphous carbon form a multilayer protection, so the entire composite LLZO particle structure has enhanced lithium conductivity, achieving better battery electrode material manufacturing quality. In the present application, the functional group can also be referred to as a functional group.

[0006] To achieve the above object, the present application provides an amine functionalized oxide ceramic particle, wherein the amine functionalized oxide ceramic particle is a plurality of composite LLZO particles, the composite LLZO particles are added to an electrode of a solid or quasi-solid battery, the electrode comprises an electrode substrate and an electrode slurry layer coated on the electrode substrate; the structure of the composite LLZO particle comprises: an LLZO particle for guiding and dispersing lithium ions through the electrode; so that the lithium ions can present a uniform channel distribution inside the electrode; a hydroxyl ion layer is coated on the outer surface of the LLZO particle, which forms a secondary LLZO particle as a whole; wherein the hydroxyl ion layer is formed by adding trimethylolamine in the process of preparing the composite LLZO particle, wherein the trimethylolamine has three OH- bonds, two of which are bonded with the oxide functional groups of the LLZO particle itself, and the third OH- bond of the trimethylolamine extends towards the outer surface of the LLZO particle, thereby forming the hydroxyl ion layer; a dopamine layer is coated on the outside of the secondary LLZO particle to form the composite LLZO particle; wherein the dopamine layer is formed by copolymerization between dopamines; the OH- bond of the dopamine itself can undergo dehydration polymerization with the third OH- bond of the hydroxyl ion layer, so that the dopamine can be combined with the secondary LLZO particle to form the composite LLZO particle as a whole; the dopamine has hydrophobic properties, which can further protect the LLZO particle from moisture. A CTAB layer is further coated on the outside of the dopamine layer, and the CTAB is a surfactant. The CTAB is mixed in the dopamine layer and the hydroxyl ion layer; the CTAB can generate attractive force with the molecules in the dopamine layer and the hydroxyl ion layer due to the polarity of the molecules. The weight ratio of the total weight of the CTAB mixed in the dopamine layer and the hydroxyl ion layer and the CTAB in the CTAB layer to the total weight of the dopamine in the dopamine layer is 0.1% to 0.3%. The CTAB is cetyltrimethylammonium bromide. The trimethylolamine can also be referred to as tris(hydroxymethyl)aminomethane (Tris).

[0007] The addition of CTAB can make the dispersion of the LLZO particles better without forming agglomeration, and reduce the possibility of lithium fluorination between the LLZO particles and the positive electrode slurry.

[0008] The dopamine material coated on the outer surface of the LLZO material has hydrophobic properties, so that moisture is less likely to enter the LLZO material. In addition, carbon nanotubes and nanoscale amorphous carbon are added to the outer surface of the LLZO material coated with dopamine material to coat the electrode particles in the electrode material of the battery, thereby improving the conductivity of the entire electrode. BRIEF DESCRIPTION OF DRAWINGS

[0009] Figure 1 A structural diagram of the present application is shown.

[0010] Figure 2 An application example of the present application is shown.

[0011] Figure 3 An enlarged schematic diagram of the hydroxide layer structure of the present application is shown.

[0012] Figure 4 A structural diagram of the tertiary LLZO particle of the present application is shown.

[0013] Figure 5 An enlarged schematic diagram of the dehydration polymerization reaction of the OH- bond of the dopamine itself and the third OH- bond of the hydroxide layer and a structural diagram thereof are shown.

[0014] Figure 6 A schematic diagram showing the attraction of the OH- bond of the CTAB and dopamine and the OH- bond of the hydroxide layer is shown.

[0015] Figure 7 A cross-sectional view showing that the dopamine layer of the present application is further coated with the CTAB layer is shown. DETAILED DESCRIPTION

[0016] The present application will be described in detail below with reference to the accompanying drawings and specific examples.

[0017] Reference is made to Figures 1 to 7 As shown, oxide ceramic particles coated with an aminated functional group of the present application are shown, wherein the particles are a plurality of composite LLZO (lithium lanthanum zirconium oxide) particles 100, which are mainly used for electrodes of solid-state or quasi-solid-state batteries, especially the positive electrode 10 of the solid-state or quasi-solid-state battery. The particle size of the composite LLZO particles 100 is between 50 nanometers and 200 nanometers.

[0018] The positive electrode 10 includes: a positive electrode substrate 11, which is a carrier plate for carrying the material of the positive electrode 10; a positive electrode slurry layer 13 coated on the positive electrode substrate 11, the positive electrode slurry layer 13 including a positive electrode slurry 12 as a binder. The positive electrode slurry layer 13 further includes: the plurality of composite LLZO particles 100. The proportion of the composite LLZO particles 100 in the electrode slurry layer (especially the positive electrode slurry layer) is between 0.5wt% and 5wt%.

[0019] The structure of a composite LLZO particle 100 in the present application is described below. The composite LLZO particle 100 includes:

[0020] The LLZO particles 15 are mainly because the LLZO material has high ionic conductivity for lithium ions. So when the lithium ions pass through the electrode, the passage of lithium ions can be dispersed by the guidance of multiple dispersed LLZO particles, so that the lithium ions can present uniform channel distribution inside the electrode, avoiding the abnormal accumulation of lithium ions in the electrode slurry and generating side reactions with the electrode slurry.

[0021] Because there is moisture in the manufacturing process of the electrode, and the LLZO particles are hydrophilic and prone to moisture to produce alkaline substances, so the outer layer of the LLZO particles must be coated with a protective layer to avoid the LLZO particles from being damp in the electrode manufacturing process.

[0022] The LLZO particles 15 are lithium lanthanum zirconium oxide (Li7La3Zr2O 12 , LLZO), or formed by doping at least one metal element (such as Li 6.2 Ga 0.8 La3Zr2O 12 , which is a gallium (Ga) doped lithium lanthanum zirconium compound, or can also be an aluminum (Al) doped or barium (Ba) doped lithium lanthanum zirconium compound).

[0023] A hydroxyl ion (OH-) layer 24 is coated on the outer surface of the LLZO particles 15, which forms a secondary LLZO particle 30 as a whole (such as Figure 3 ). The thickness of the hydroxyl ion layer 24 is between 0.5 nanometers and 2 nanometers. The hydroxyl ion layer 24 is composed of adding trimethylamine in the process of the composite LLZO particle 100, wherein the trimethylamine itself has three OH- bonds, and two of the OH- bonds in the trimethylamine are used to form hydrogen bonds with the oxidation functional groups on the LLZO particles 15, and the third OH- bond of the trimethylamine extends towards the outer surface of the LLZO particles 15, thereby forming the hydroxyl ion layer 24 (such as Figure 3 ). Only two trimethylamine molecules are shown in the figure, which is only for illustration and does not limit the scope of the present application.

[0024] A dopamine layer 35 is coated on the outside of the secondary LLZO particle 30, and the composite LLZO particle 100 is formed (such as Figure 1 ). Each dopamine will produce a copolymerization reaction, so the dopamine layer 35 can be formed. The OH- bond of the dopamine itself will produce a dehydration polymerization reaction with the third OH- bond of the hydroxyl ion layer 24, so that the dopamine can be combined with the secondary LLZO particle 30 to form the composite LLZO particle 100 as a whole (such as Figure 5 ). The thickness of the dopamine layer 35 is between 1 nanometer and 10 nanometers.

[0025] The purpose of coating the secondary LLZO particles 30 with the dopamine layer 35 is that moisture is present during the manufacturing process of the electrode paste. Since the LLZO particles 15 are hydrophilic, they are easily affected by moisture, producing alkaline byproducts that compromise their lithium conductivity. Dopamine, on the other hand, is hydrophobic; therefore, coating the secondary LLZO particles 30 with the dopamine layer 35 further protects them from moisture absorption.

[0026] The purpose of applying the hydroxide ion layer 24 to coat the outer surface of the LLZO particles 15 is because hydroxide ions (OH-) are polar. Therefore, by coating the hydroxide ion layer 24, they can react with the dopamine material of the dopamine layer 35, so that the dopamine material can better adhere to the secondary LLZO particles 30.

[0027] like Figure 6 and Figure 7 As shown, the dopamine layer 35 is further coated with a CTAB (cetyltrimethylammonium bromide) layer 61, which is composed of multiple CTAB 60s. CTAB is a surfactant. Multiple CTAB 60s are also mixed within the dopamine layer 35 and the hydroxide ion layer 24.

[0028] The weight ratio of the total weight of CTAB 60 mixed in the dopamine layer 35 and the hydroxide ion layer 24 and the total weight of CTAB 60 in the CTAB layer 61 to the total weight of dopamine in the dopamine layer 35 is between 0.1% and 0.3%.

[0029] The distribution ratio of CTAB 60 in the dopamine layer 35, the hydroxide ion layer 24, and the CTAB layer 61 is a natural result of the manufacturing process. A portion of the CTAB 60 is mixed within the dopamine layer 35 and the hydroxide ion layer 24, while the remainder forms another coating layer (i.e., the CTAB layer 61) around the dopamine layer 35. The CTAB molecules exert an attractive force due to their polarity against molecules with opposite polarities in the dopamine layer 35 and the hydroxide ion layer 24.

[0030] The addition of CTAB can make the dispersion of the LLZO particles 15 better without forming agglomeration, reducing the possibility of lithium fluorination of the LLZO particles 15 with PVDF (polyvinylidene fluoride) in the positive electrode slurry. The charge of the LLZO particles 15 is concentrated if they are not agglomerated. Among them, during the modification process of the LLZO particles 15, local exposed OH- bonds (the third OH- bond of the hydroxyl ion layer 24 or the OH- bond of the dopamine layer 35 itself) may occur on the surface of the LLZO particles 15, the CTAB is positively charged and negatively charged (such as Figure 6 ), and the positively charged CTAB can have an attractive force with the exposed OH- bond of the composite LLZO particles 100, and the overall charge does not change the overall electrical properties, not only improves the integrity of the surface coating, but also does not cause agglomeration of dopamine, and the composite LLZO particles 100 are not exposed to avoid alkalinity.

[0031] Among them, during the manufacturing process, not all of the third OH- bonds of the hydroxyl ion layer 24 will undergo dehydration polymerization with the OH- bonds of dopamine itself, so there are still exposed OH- bonds, and the CTAB can have an attractive force with the exposed OH- bonds, or the CTAB can have an attractive force with the OH- bonds of dopamine itself, so the overall structure is a layer-by-layer protective structure, and the overall coating is more complete.

[0032] The present application also includes: a plurality of carbon nanotubes 42 (CNT, Carbon Nanotube) and a plurality of nanometer-sized amorphous carbon 45, which are coated on the composite LLZO particles 100 to form a tertiary LLZO particles 50 (such as Figure 4 ). Among them, the size of the carbon nanotubes 42 is between 200 nanometers and 500 nanometers, and the size of the nanometer-sized amorphous carbon 45 is between 10 nanometers and 40 nanometers. The nanometer-sized amorphous carbon 45 is, for example, a super P conductive aid.

[0033] Among them, in the tertiary LLZO particles 50, the weight ratio of the total weight of the plurality of carbon nanotubes 42 and the nanometer-sized amorphous carbon 45 to the total weight of the LLZO particles 15 (i.e. single LLZO particles 15) is 0.2-2:99.8-98.

[0034] The nanometer-sized amorphous carbon 45 is also a conductive aid like the carbon nanotubes 42. Among them, because the nanometer-sized amorphous carbon 45 is in the form of particles, and the carbon nanotubes 42 are in the form of long strips, the carbon nanotubes 42 are arranged vertically and horizontally, and gaps are formed between them. These gaps cannot conduct current, so adding the nanometer-sized amorphous carbon 45 in the gaps can make the charge jump through the nanometer-sized amorphous carbon 45 to the next carbon nanotube 42, thus further increasing the transmission of current.

[0035] The carbon nanotubes 42 have the advantage that lithium ions can be easily stabilized between the carbon nanotubes 42, so that the electrode slurry in the present application can stably hold a large number of lithium ions, thereby improving the overall conductivity of lithium ions, and electrons can be easily fixed between the carbon nanotubes 42, thereby improving the overall conductivity of lithium ions. Furthermore, because the ion conductivity is very high, it helps the entire battery to be quickly charged and quickly discharged, and in addition, the amount of cobalt used can be reduced, thereby reducing the overall production cost.

[0036] In the present application, a dopamine layer is coated on the outer surface of the secondary LLZO particles, and the dopamine layer has hydrophobic properties, so that the dopamine layer coated on the outer surface of the secondary LLZO particles makes it more difficult for moisture to enter the LLZO particles. The present application also coats the nanoscale amorphous carbon and the carbon nanotubes as a conductive aid on the outside of the composite LLZO particles. The nanoscale amorphous carbon is in the form of particles, and the carbon nanotubes are in the form of long strips. The addition of the nanoscale amorphous carbon in the voids helps the overall structure to have better conductivity. In the present application, the dopamine layer, CTAB, the plurality of carbon nanotubes, and the nanoscale amorphous carbon form a multilayer protection, so that the overall composite LLZO particle structure has enhanced lithium conductivity, and the electrode manufacturing process avoids reaction with the materials in the electrode slurry, achieving better battery electrode material manufacturing quality.

[0037] In summary, the present application is a humanized and thoughtful design that meets the actual needs. It specifically improves the existing deficiencies and has obvious breakthrough advantages compared to the prior art. It indeed has improved efficiency and is not easy to achieve.

[0038] The above is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. Oxide ceramic particles coated with aminated functional groups, characterized in that, The oxide ceramic particles coated with amine functional groups are composite LLZO particles, wherein LLZO is lithium lanthanum zirconium oxide or lithium lanthanum zirconium oxide doped with at least one metal element, the composite LLZO particles are added to an electrode of a solid or quasi-solid battery, the electrode comprises an electrode substrate and an electrode slurry layer coated on the electrode substrate; the structure of the composite LLZO particles comprises: The LLZO particles are used to guide and disperse lithium ions through the electrode; thus, the lithium ions can be evenly distributed in the electrode; A hydroxyl ion layer is coated on the outer surface of the LLZO particles, which forms a secondary LLZO particle; wherein the hydroxyl ion layer is formed by adding trimethylolamine in the process of the composite LLZO particles, wherein the trimethylolamine has three OH- bonds, two of which are used to bond with the oxide functional groups of the LLZO particles, and the third OH- bond of the trimethylolamine extends towards the outer surface of the LLZO particles, thereby forming the hydroxyl ion layer; A dopamine layer is coated on the outside of the secondary LLZO particle to form the composite LLZO particle; because dopamine can undergo copolymerization, the dopamine layer can be formed; the OH- bonds of the dopamine can undergo dehydration polymerization with the third OH- bond of the hydroxyl ion layer, so that the dopamine can be combined with the secondary LLZO particle to form the composite LLZO particle; the dopamine has hydrophobic properties, which can further protect the LLZO particle from moisture.

2. The amine-functionalized, oxide ceramic particle coated with amine functional groups of claim 1, wherein, The dopamine layer is further coated with a CTAB layer, and the CTAB is a surfactant.

3. The amine-functionalized, oxide ceramic coated particle of claim 2, wherein, The CTAB is mixed in the dopamine layer and the hydroxyl ion layer. The CTAB can attract molecules with different polarities in the dopamine layer and the hydroxyl ion layer.

4. The amine-functionalized, oxide ceramic coated particle of claim 3, wherein, The weight ratio of the total weight of the CTAB mixed in the dopamine layer and the hydroxyl ion layer and the CTAB in the CTAB layer to the total weight of the dopamine in the dopamine layer is between 0.1% and 0.3%. The addition of CTAB can improve the dispersibility of the LLZO particles without forming agglomerates, and reduce the possibility of lithium fluorination between the LLZO particles and the positive electrode slurry.

5. The amine-functionalized- group-coated-oxide ceramic particles according to claim 1, wherein, The composite LLZO particles are used in a positive electrode.

6. The amine-functionalized- group-coated-oxide ceramic particles according to claim 1, wherein, The particle size of the LLZO particles is between 50 nm and 200 nm.

7. The amine-functionalized- group-coated-oxide ceramic particles according to claim 1, wherein, The thickness of the hydroxyl ion layer is between 0.5 nm and 2 nm. The thickness of the dopamine layer is between 1 nm and 10 nm.

8. The amine-functionalized- group-coated-oxide ceramic particles according to claim 1, wherein, Further comprising: carbon nanotubes and nanoscale amorphous carbon coated on the outer surface of the composite LLZO particles to form a tertiary LLZO particle.

9. The amine-functionalized oxide ceramic particle coated with an amine-functional group according to any one of claims 1 to 3, characterized in that, The size of the carbon nanotubes is between 200 nm and 500 nm; the size of the nanoscale amorphous carbon is between 10 nm and 40 nm.

10. The amine-functionalized, oxide ceramic coated particle of claim 9, wherein, ​ 11. The amine-functionalized, oxide ceramic coated particle of claim 9, wherein, wherein in the tertiary LLZO particles, the weight ratio of the total weight of the plurality of carbon nanotubes and the nanoscale amorphous carbon to the total weight of the LLZO particles is 0.2-2: 99.8-98.

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