Positive electrode plate containing composite ceramic particles coated with organic matter

Abstract

A positive electrode plate is provided that contains composite ceramic particles coated with an organic material. [Solution] The battery includes a positive electrode substrate (21) and a positive electrode slurry layer (23) applied to the positive electrode substrate, the positive electrode slurry layer being composed of a positive electrode slurry (22). The positive electrode slurry includes a plurality of positive electrode particles (10) for storing or releasing lithium ions, a polymer adhesive (12), a plurality of conductive materials (14) for increasing the conductivity of the positive electrode slurry as a whole, and a plurality of composite ceramic particles (100) for guiding lithium ions to prevent abnormal accumulation of lithium ions in the positive electrode slurry and side reactions with the positive electrode slurry. Each composite ceramic particle includes ceramic particles, a dopamine layer that coats the outer surfaces of the ceramic particles and forms primary particles, and a PVDF layer that coats the outer surfaces of the primary particles. The ceramic particles having the dopamine layer and the PVDF layer form the corresponding composite ceramic particle.

Description

[Technical Field]

[0001] The present invention relates to a positive electrode plate, and more particularly to a positive electrode plate containing composite ceramic particles coated with an organic material. [Background technology]

[0002] Batteries are typically constructed by placing a positive electrode and a negative electrode in an electrolyte solution, and conventional technologies have increased ionic conductivity by adding ceramic particles to the positive electrode. Because ceramic particles have high ionic conductivity for lithium ions, lithium ions are guided by the dispersed ceramic particles as they pass through the positive electrode, creating lithium ion channels, resulting in a uniform distribution of lithium ions within the positive electrode. Summary of the Invention [Problem to be solved by the invention]

[0003] However, the surface of conventional ceramic particles contains a large amount of alkaline functional groups (e.g., OH -, Li2O), when conventional ceramic particles are added to an electrode slurry during the manufacturing process, the alkaline functional groups of the ceramic particles react with the solvent in the electrode slurry, resulting in a strongly alkaline electrode slurry. This causes deterioration of the electrode particles and electrode slurry, impacting the manufacturing process and making it difficult to achieve the expected electrochemical properties of the manufactured electrode plate. Conventional techniques have involved coating the outer surfaces of the ceramic particles with a dopamine layer to protect them, but the dopamine layer does not completely cover the outer surfaces of the ceramic particles, leaving some of the ceramic particle surfaces exposed. The solvent is added during the manufacturing of the electrode slurry. When the electrode slurry is applied to an electrode substrate and subsequent processes are performed, the solvent originally present in the electrode slurry evaporates, forming an electrode slurry layer from the electrode slurry, which adheres to the electrode substrate to form an electrode plate. That is, the solvent is no longer present in the electrode slurry layer.

[0004] After extensive research, the inventors have found that by adopting a positive electrode plate that contains composite ceramic particles coated with a novel organic material, ceramic particles further coated with a PVDF layer are applied to the electrode slurry, preventing the exposed ceramic particles from reacting with the solvent in the electrode slurry, thereby solving the above-mentioned shortcomings of the prior art.

[0005] The present invention was developed through intensive research by the inventors in consideration of the above problems, and its purpose is to provide a positive electrode plate to which composite ceramic particles coated with an organic substance are added. [Means for solving the problem]

[0006] In order to achieve the above object, a positive electrode plate to which composite ceramic particles coated with an organic substance, which is one embodiment of the present invention, is added, a positive electrode substrate that is a substrate for placing a positive electrode material; a positive electrode slurry layer that is applied to the positive electrode substrate and is made of a positive electrode slurry; The positive electrode slurry is a plurality of positive electrode particles for storing or releasing lithium ions, the positive electrode particles being an active material; an adhesive that is a polymer material; a plurality of conductive materials for increasing the conductivity of the entire positive electrode slurry; a plurality of composite ceramic particles for guiding lithium ions to disperse lithium ion channels so as to prevent abnormal accumulation of lithium ions in the positive electrode slurry and the occurrence of side reactions with the positive electrode slurry; Each of the composite ceramic particles is Ceramic particles; a dopamine layer (a layer containing polydopamine) that coats the outer surfaces of the ceramic particles and forms primary particles; a PVDF layer covering the outer surface of the primary particles, wherein the ceramic particles having the dopamine layer and the PVDF layer form corresponding composite ceramic particles; The positive electrode particles are distributed in the positive electrode slurry layer in a dispersed manner, the conductive material and the composite ceramic particles are dispersed among the positive electrode particles, and the adhesive is used to bond the above-mentioned materials in the positive electrode slurry. [Effects of the Invention]

[0007] In the present invention, the outer surfaces of the ceramic particles, which are originally coated with the dopamine layer, are further coated with the PVDF layer as a protective layer, thereby further protecting the internal primary particles. In this way, when the composite ceramic particles are added to a solvent-containing positive electrode slurry during the process of manufacturing the positive electrode plate, they do not react with the solvent in the positive electrode slurry, preventing degradation of the positive electrode slurry. Therefore, the overall stability of the positive electrode slurry containing the composite ceramic particles is further improved.

[0008] At least the following points will become clear from the description and drawings to be described later. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows an embodiment of a positive electrode plate to which organic-coated composite ceramic particles according to the present invention are added. [Figure 2] 1 is a cross-sectional view of a composite ceramic particle according to the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below with reference to the accompanying drawings, in which: FIG. 1 is a block diagram of a conventional optical fiber cable; FIG. 2 is a block diagram of a conventional optical fiber cable;

[0011] First, an example of a specific embodiment of a positive electrode plate to which composite ceramic particles coated with an organic substance according to the present invention are added will be described with reference to FIGS.

[0012] The positive electrode plate containing the organic-coated composite ceramic particles of the present invention mainly includes the following components:

[0013] The positive electrode 20 is a positive electrode substrate 21 that is a substrate for placing the material of the positive electrode 20; a positive electrode slurry layer 23 applied to the positive electrode substrate 21 and composed of a positive electrode slurry 22; The positive electrode slurry 22 is a plurality of positive electrode particles 10 for storing or releasing lithium ions, the plurality of positive electrode particles 10 being at least one selected from the group consisting of lithium cobalt oxide (LCO) particles and nickel cobalt manganese (NCM) particles, the plurality of positive electrode particles 10 being an active material, and the ratio of the plurality of positive electrode particles 10 to the entire positive electrode slurry layer 23 being in the range of 92 wt % to 98 wt %; an adhesive 12 made of a polymer material, which is at least one selected from the group consisting of PVDF (Polyvinylidene Fluoride) and PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropene); a plurality of conductive materials 14, each of which is at least one selected from the group consisting of carbon nanotubes, nanoscale amorphous carbon, and graphene, wherein the nanoscale amorphous carbon is, for example, superP, and the conductive materials 14 are used to enhance the electronic conductivity of the positive electrode slurry 22; and a plurality of composite ceramic particles 100 for guiding lithium ions to disperse lithium ion channels to prevent abnormal accumulation of lithium ions in the positive electrode slurry 22 and the occurrence of side reactions with the positive electrode slurry 22.

[0014] Each of the composite ceramic particles is Ceramic particles 15 having a particle size of less than 100 nm; a dopamine layer 35 coating the outer surface of the ceramic particles to form primary particles 110; The ceramic particles 15 having the dopamine layer 35 and the PVDF layer 41 form the corresponding composite ceramic particles 100, and the thickness of the PVDF layer 36 is in the range of 10 nm to 100 nm, the thickness of the dopamine layer 34 is in the range of 2 nm to 15 nm, and the overall particle size of the composite ceramic particles 30 is less than 300 nm.

[0015] The positive electrode particles 10 are distributed in the positive electrode slurry layer 23 in a dispersed manner, and the conductive material 14 and the composite ceramic particles 100 are dispersed among the positive electrode particles 10. The adhesive 12 is used to bond the above-mentioned materials in the positive electrode slurry 22.

[0016] The ceramic particles 15 have a lithium ion conducting ability (an ion conductivity of 10 -5 cm 2 The oxide is at least one of a ceramic oxide having a diffusion coefficient (diffusion coefficient) of more than 1 / s, an oxide having a garnet structure, or an oxide having a perovskite structure.

[0017] The ceramic oxide having lithium ion conductivity is, for example, lithium aluminum germanium phosphate (LAGP) having a NASICON (sodium (Na) superionic conductor) structure, and the oxide having a garnet structure is, for example, lithium lanthanum zirconium oxide (Li7La3Zr2O 12 The oxide having a perovskite structure is, for example, lithium lanthanum zirconium oxide (LLZO), and the oxide having a perovskite structure is, for example, lithium lanthanum titanium oxide (LLTO).

[0018] When the ceramic particles 15 are made of LLZO, the LLZO material is formed from at least one selected from the group consisting of LLZO, Ga-LLZO (Ga-doped LLZO, gallium-doped lithium-lanthanum-zirconium oxide), Cu-LLZO (Cu-doped LLZO, copper-doped lithium-lanthanum-zirconium oxide), Ta-LLZO (Ta-doped LLZO, tantalum-doped lithium-lanthanum-zirconium oxide), Sr-LLZO (Sr-doped LLZO, strontium-doped lithium-lanthanum-zirconium oxide), and Al-LLZO (Al-doped LLZO, aluminum-doped lithium-lanthanum-zirconium oxide).

[0019] When the ceramic particles 15 are made of LAGP, the LAGP is Li 1+x Al x Ge2-x (PO4)3, or Li 1+x+y Al x Ge 2-x-y-z M y N z (PO4)3, where x is in the range of 0.1 to 0.8, y is in the range of 0 to 0.2, and z is in the range of 0 to 0.2. M is selected from Sc 3+ (Scandium ion), Y 3+ (yttrium ion), Ga 3+ (Gallium ion), In 3+ (indium ion), La 3+ (lanthanum ion) and other trivalent cations. 4+ (zirconium ion), Si 4+ (silicon ion), Sn 4+ (tin ion) and other tetravalent cations.

[0020] The positive electrode slurry 22 further includes a lithium salt 16, which is at least one selected from the group consisting of LiTFSI (LiN(CF3SO2)2, lithium bis(trifluoromethanesulfonyl)imide), LiFSI (lithium bis(fluorosulfonyl)imide), LiF (lithium fluoride), and BMITFSI (1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide). The lithium salt 16 is used to improve electrochemical properties.

[0021] The weight ratio between the polymer material (i.e., the adhesive 12) and the plurality of positive electrode particles 10 is in the range of 0.005 to 0.035. The weight ratio between the plurality of conductive materials 14 and the plurality of positive electrode particles 10 is in the range of 0.005 to 0.028. The weight ratio between the plurality of composite ceramic particles 100 and the plurality of positive electrode particles 10 is in the range of 0.001 to 0.016. The weight ratio between the lithium salt 16 and the plurality of positive electrode particles 10 is in the range of 0.002 to 0.028.

[0022] In conventional electrode plate manufacturing techniques, the outer surfaces of ceramic particles are coated with the dopamine layer to protect the ceramic particles, but the dopamine layer does not completely cover the outer surfaces of the ceramic particles, leaving some of the ceramic particle surfaces exposed. Furthermore, in conventional electrode plate manufacturing techniques, after adding a plurality of ceramic particles coated with the dopamine layer to a positive electrode slurry, the exposed portions of the ceramic particles interact with the solvent added to the positive electrode slurry, causing the positive electrode slurry to become strongly alkaline.

[0023] Although the embodiment of the present invention has been described above in detail with reference to the drawings, the specific configuration is not limited to this embodiment, and design modifications and the like are also included within the scope of the present invention without departing from the gist of the present invention. [Explanation of symbols]

[0024] 10 positive electrode 11 Positive substrate 12 Positive electrode slurry 13 Positive electrode slurry layer 15 Ceramic particles 35 Dopamine layer (layer containing polydopamine) 41 PVDF layer 100 Composite conductive particles 110 Secondary composite particles

Claims

1. a positive electrode substrate that is a substrate for placing a positive electrode material; a positive electrode slurry layer that is applied to the positive electrode substrate and is made of a positive electrode slurry; The positive electrode slurry is a plurality of positive electrode particles for storing or releasing lithium ions, the positive electrode particles being an active material; an adhesive that is a polymer material; a plurality of conductive materials for increasing the conductivity of the entire positive electrode slurry; a plurality of composite ceramic particles for guiding lithium ions to disperse lithium ion channels so as to prevent abnormal accumulation of lithium ions in the positive electrode slurry and the occurrence of side reactions with the positive electrode slurry; Each of the composite ceramic particles is Ceramic particles; a dopamine layer coating the outer surface of the ceramic particles to form primary particles; a PVDF layer covering an outer surface of the primary particles, the ceramic particles having the dopamine layer and the PVDF layer forming corresponding composite ceramic particles; a positive electrode plate containing composite ceramic particles coated with an organic substance, wherein the positive electrode particles are distributed in the positive electrode slurry layer in a dispersed manner, the conductive material and the composite ceramic particles are dispersed among the positive electrode particles, and the adhesive is used to adhere the above-mentioned materials in the positive electrode slurry.

2. The positive electrode plate according to claim 1 , wherein the positive electrode slurry further contains a lithium salt for enhancing electrochemical properties.

3. 3. The positive electrode plate according to claim 2, wherein the lithium salt is at least one selected from the group consisting of LiTFSI, LiFSI, and BMITFSI.

4. 2. The positive electrode plate according to claim 1, wherein the positive electrode particles are at least one selected from the group consisting of lithium cobalt oxide particles and nickel-cobalt-manganese particles.

5. The positive electrode plate to which the composite ceramic particles coated with an organic substance according to claim 1 are added, characterized in that the weight ratio between the polymer material and the plurality of positive electrode particles is in the range of 0.005 to 0.035, the weight ratio between the plurality of conductive materials and the plurality of positive electrode particles is in the range of 0.005 to 0.028, and the weight ratio between the plurality of composite ceramic particles and the plurality of positive electrode particles is in the range of 0.001 to 0.

016.

6. The positive electrode plate to which the composite ceramic particles coated with an organic material according to claim 2 are added, characterized in that the weight ratio of the lithium salt to the plurality of positive electrode particles is in the range of 0.002 to 0.

028.

7. 2. The positive electrode plate according to claim 1, wherein the polymer material is at least one selected from the group consisting of PVDF and PVDF-HFP.

8. 2. The positive electrode plate according to claim 1, wherein the conductive material is at least one selected from the group consisting of carbon nanotubes, nanoscale amorphous carbon, and graphene.

9. 2. The positive electrode plate according to claim 1, wherein the particle size of each of the composite ceramic particles is less than 300 nm.

10. 2. The positive electrode plate according to claim 1, wherein the ceramic particles are at least one of a ceramic oxide having lithium ion conductivity, an oxide having a garnet structure, and an oxide having a perovskite structure.

11. The positive electrode plate according to claim 10, wherein the ceramic oxide is selected from the group consisting of germanium aluminum lithium phosphate having a NASICON structure.

12. When the ceramic particles are composed of LAGP, the LAGP is Li １＋ｘ Al ｘ Ge ２-ｘ (P.O. ４ ) ３ , or Li １＋ｘ＋ｙ Al ｘ Ge ２-ｘ-ｙ-ｚ M ｙ N ｚ (P.O. ４ ) ３ wherein x is in the range of 0.1 to 0.8, y is in the range of 0 to 0.2, z is in the range of 0 to 0.2, M is a trivalent cation, and N is a tetravalent cation.

13. The trivalent cation is Sc ３＋ (Scandium ion), Y ３＋ (yttrium ion), Ga ３＋ (Gallium ion), In ３＋ (indium ions), and La ３＋ (lanthanum ion), and the tetravalent cation is selected from Zr ４＋ (zirconium ion), Si ４＋ (silicon ions), and Sn ４＋ 13. The positive electrode plate to which the composite ceramic particles coated with an organic substance according to claim 12 are added, wherein the organic ions are selected from the group consisting of tin ions and tin ions.

14. The positive electrode plate to which the composite ceramic particles coated with an organic substance according to claim 10 is added, characterized in that the oxide having the garnet structure is lithium-lanthanum-zirconium oxide, and the oxide having the perovskite structure is lithium-lanthanum-titanium oxide.

15. 2. The positive electrode plate to which the composite ceramic particles coated with an organic substance according to claim 1 are added, wherein when the ceramic particles are composed of LLZO, the LLZO material is at least one selected from the group consisting of LLZO, Ga-LLZO, Cu-LLZO, Ta-LLZO, Sr-LLZO, and Al-LLZO.

Images