Negative electrode plate with dry electrode mass material containing ceramic particles with a nasicon structure, manufactured independently of the battery substrate.

Abstract

Negative electrode plate with dry electrode mass material containing NASICON structural ceramic particles and manufactured independently of the battery substrate; the negative electrode plate is used in a solid-state or semi-solid-state battery. The negative electrode plate includes: a negative electrode substrate that serves as a support material for the negative electrode; a negative electrode mass layer that adheres to the negative electrode substrate and forms the negative electrode plate; the negative electrode mass layer consists of the dry electrode mass material; The dry electrode mass material comprises: A multitude of negative electrode particles, which serve to store or release lithium ions, each of the negative electrodes representing an active material; Several PEOs (polyethylene oxides) serve to guide lithium ions and increase the lithium ion conductivity of the negative electrode. The PEOs are thermoplastic and therefore melt at high temperatures. Several CMCs (carboxymethylcelluloses) are formed from polymer materials. A copolymer formed from PEOs and CMCs is melted, resulting in a sticky dry electrode material. This sticky, dry electrode material adheres to the substrate of the negative electrode, thus forming the negative electrode plate. The dry electrode mass material also contains: Several conductive agents to increase the electrical conductivity of the dry electrode mass material; Several lithium salts are used to improve the electrochemical quality of the battery. The lithium salts facilitate the sliding of the polymer chains within the polymer material and increase the conductivity of the ions. a multitude of ceramic composite particles which serve to guide the lithium ions to dispersed lithium ion channels in order to prevent side reactions between the lithium ions and the dry electrode mass material due to abnormal deposition of lithium ions in the dry electrode mass material; and The negative electrode particles, the composite ceramic particles, the conductivity agents, and the lithium salts are dispersed in the polymer material of the dry electrode compound. The dry electrode compound and the negative electrode substrate can be produced simultaneously. The dry electrode compound melts at high temperatures and then adheres to the negative electrode substrate. Using the dry electrode compound eliminates the drying and rolling steps in the manufacturing process. The dry electrode compound is independent of the negative electrode substrate and can be applied separately. During production, the dry electrode compound is melted and then bonded to the negative electrode substrate at high temperature to form the negative electrode plate.

Description

AREA OF INVENTION

[0001] The invention relates to a negative electrode plate, in particular a negative electrode plate with dry electrode mass material which contains ceramic particles with NASICON structure and is produced independently of a battery substrate. BACKGROUND OF THE INVENTION

[0002] According to the current state of the art, a negative electrode consists of a substrate and a layer of negative electrode material applied to it. The negative electrode material layer is formed by the negative electrode material itself. The negative electrode material contains: several negative electrode particles that can store or release lithium ions, several polymers, including CMCs (carboxymethylcelluloses), a solvent for dispersing the negative electrode sludge (water), several conductive agents to increase electrical conductivity, and several ceramic particles to guide the lithium ions in the dispersed lithium ion channels.

[0003] According to the current state of the art, the solvent is added during the production of the negative electrode compound to ensure even distribution of the material. The negative electrode compound, along with the solvent, is then applied to the substrate and subsequently dried to remove the solvent. The evaporation of the solvent creates holes in the negative electrode layer, necessitating an additional rolling step. This ensures a strong bond between the negative electrode compound layer and the negative electrode substrate.

[0004] However, since current technology requires drying and rolling steps to coat the negative electrode mass with solvent, manufacturing costs are high. Furthermore, the rolling step can lead to material breakage in the negative electrode mass layer, which reduces the overall battery quality.

[0005] The invention therefore aims to solve this problem in the prior art by using PEOs in the dry electrode mass material. This eliminates drying and rolling steps in the manufacturing process and reduces manufacturing costs. SUMMARY OF THE INVENTION

[0006] To overcome the aforementioned shortcomings of the prior art, the object of the invention is to provide a negative electrode plate with a dry electrode mass material containing ceramic particles with a NASICON structure, manufactured independently of a battery substrate. The PEOs are thermoplastic, allowing them to melt at high temperatures and then adhere to the negative electrode substrate. The use of thermoplastic PEOs eliminates the need for drying and rolling steps to remove the solvent from the negative electrode mass. This eliminates the drying step and prevents material breakage during rolling. Furthermore, this manufacturing process extends the shelf life of the negative electrode plate. BRIEF DESCRIPTION OF THE IMAGES Fig. shows a schematic representation of the structure of the invention. Fig. The cross-sectional view shows the structure of the ceramic composite particle according to the invention. Fig. The cross-sectional view shows the structure of the ceramic composite particle according to the invention with the ZnO layer enclosed therein. DETAILED DESCRIPTION OF THE INVENTION

[0007] According to the Fig. This concerns a negative electrode plate with a dry electrode mass material containing ceramic particles with a NASICON structure, manufactured independently of the battery substrate. A solid-state or semi-solid-state battery comprises a negative electrode 20. The negative electrode 20 consists of the following elements: A negative electrode substrate 21 serves as a support material for the negative electrode 20. The negative electrode substrate 21 is designed as a copper foil.

[0008] A negative electrode slurry layer 23 is applied to the negative electrode substrate 21 to form a negative electrode plate. According to the invention, the negative electrode slurry layer 23 consists of the dry electrode material 22. The dry electrode material 22 is produced independently of the negative electrode substrate 21 and can be applied separately. In application, the dry electrode material 22 is melted and then applied to the negative electrode substrate 21 at a high temperature.

[0009] The dry electrode mass material 22 comprises the following elements: A variety of negative electrode particles 15 serve to store or release lithium ions. The negative electrode particles 15 consist of at least one of the following materials: carbon materials (such as graphite, hard carbons, soft carbons, etc.), Si-C composites, SiOx-C composites, etc. Each of the negative electrode particles 15 constitutes an active material. The weight fraction of the negative electrode particles 15 in the dry electrode mass material 22 is between 90 and 95 wt.%, where wt.% indicates the weight fraction. A variety of PEOs (polyethylene oxides) serve to guide lithium ions and increase the lithium ion conductivity of the negative electrode. The PEOs are thermoplastic, meaning they melt at high temperatures and are therefore already in a molten state. The polymer material 17 consists of several CMCs (carboxymethylcelluloses). Thanks to the thermoplastic properties of the PEOs, the dry electrode material 22 can be melted and then applied to the substrate 21 of the negative electrode at high temperatures. Using the dry electrode material 22 eliminates the need for conventional solvents. This eliminates drying and rolling steps in the manufacturing process. As a result, manufacturing costs are reduced and material fractures in layer 23 of the negative electrode slurry caused by rolling are prevented. This also extends the potential shelf life of the negative electrode plate. The polymer material 17 also contains at least one of the following substances: PVAs (polyvinyl alcohols) and SBRs (styrene-butadiene rubbers). PVAs and PEOs are compatible. PVAs and PEOs reduce the possibility of crystallization of the dry electrode mass material 22, thus ensuring firm adhesion to the negative electrode substrate 21. SBRs exhibit high toughness and therefore contribute to the strength and stability of the negative electrode plate. PEOs are thermoplastic, meaning they melt at high temperatures and then adhere to the negative electrode substrate 21. The thermoplastic nature of the PEOs eliminates drying and rolling steps in the manufacturing process and prevents the material in the negative electrode mass layer 23 from breaking during rolling. The dry electrode mass material 22 also contains: A variety of conductive materials 13, selected from at least one of the following materials: carbon nanotubes, graphene, and amorphous carbon, where the amorphous carbon can be, for example, Super P. The conductive materials 13 serve to increase the electrical conductivity of the dry electrode mass material 22. The conductive agents 13 also contain sinapic acid as a dispersant. Sinapic acid is polarizable and can therefore be combined with the oxides of the dry electrode mass material 22 to adjust the alkalinity of the polymer material 17. Thus, the sinapic acid prevents material damage caused by the high alkalinity of the polymer material 17. The weight fraction of sinapic acid in the conductive agents 13 is between 0.05 and 0.3 wt.%. Several lithium salts 19 serve to improve the electrochemical quality of the battery. The lithium salts 19 are selected from at least one of the following substances: PDDA-TFSI (poly(diallyldimethylammonium)-bis(trifluoromethanesulfonyl)imide) and Py14-TFSI. The lithium salts 19 serve to facilitate the sliding of the polymer chain of the polymer material 17 and increase the conductivity of the ion. The lithium salts 19 also contain at least one of the following substances: LiBOB, Li3PO4, LiFSI (Lithium bis(fluorosulfonyl)imide), LiTFSI(LiN(CF3SO2)2 or LiPF6. LiTFSI increases the conductivity of the lithium ions, while LiBOB prevents erosion of the LiTFSI by water and attack by hydrofluoric acid (HF), which could impair battery quality. HF is formed by the reaction of LiTFSI with water. LiBOB also allows the lithium salt 19 to be exposed to a higher voltage difference. This makes the polymer material 17 in the negative electrode more stable. A multitude of composite ceramic particles 100 conduct the lithium ions to dispersed lithium ion channels, thus preventing side reactions between the lithium ions and the dry electrode mass material 22 due to an abnormal deposition of lithium ions in the dry electrode mass material 22. Referring to the Fig. The negative electrode particles 15, the composite ceramic particles 100, the conductive agents 13 and the lithium salts 19 are dispersed in the polymer material 17 of the dry electrode mass material 22.

[0010] The weight ratio of the negative electrode particles 15, the polymer 17, and the lithium salts 19, as well as the conductive substances 13 and the composite ceramic particles 100, is 90-95:8-4:2-1. The ratio of negative electrode particles 15, polymer 17, and lithium salts 19, as well as conductive substances 13 and composite ceramic particles 100, is A:B:C. Here, A is in the range of 90-95, B in the range of 8-4, and C in the range of 2-1. The values ​​of A, B, and C within the aforementioned ranges are permissible according to the invention. In this description, the same uses as defined above have the same meaning.

[0011] Referring to Fig. Each of the composite ceramic particles comprises 100: A ceramic particle 105; A hydroxide ion layer (OH-) 110 surrounds the outer surface of the ceramic particle 105, thus forming a second composite particle 120.

[0012] A dopamine layer 130 surrounds the outer surface of the second composite particle 120, thus forming the ceramic composite particle 100.

[0013] The hydroxide ion layer 110 consists of TRIS (tris(hydroxymethyl)aminomethane, ((HOCH2)3CNH2), which is added during the manufacturing process of the ceramic composite particles 100. Each TRIS molecule contains three OH groups. - Ions: a first OH - ion, a second OH - ion and a third OH - Ion. The first and second OH -Ions of the TRIS molecules are bound to the oxidizing functional groups of the corresponding ceramic particle 105 via hydrogen bonds. The third OH ions of the TRIS molecules extend outwards to the outer surface of the corresponding ceramic particle 105 and form the hydroxide ion layer 110 there. The dopamine layer 130 consists of several copolymerized dopamine molecules. The corresponding dopamine molecules are copolymerized to form the dopamine layer 130, which is applied to the outer surface of the second composite particle 120. The OH - Ions of the dopamine molecules are attached to the third OH group by dehydration condensation. - Ions of the TRIS molecules are bound, allowing the dopamine molecules to react with the second composite particle 120. The dopamine molecules of the dopamine layer 130 are hydrophobic to protect the ceramic particle 105 and prevent its damping.

[0014] The particle size of the ceramic particle 105 is between 50 nm and 200 nm. The thickness of the hydroxide ion layer 110 is 0.5 nm to 2 nm; the thickness of the dopamine layer 130 is 1 nm to 10 nm.

[0015] As in Fig. As shown, the outer surface of the corresponding dopamine layer 130 of the ceramic composite particle 100 is additionally encased by a ZnO (zinc oxide) layer 140. The ZnO layer 140 consists of several ZnO ions. The ZnO ions of the ZnO layer 140 are hydrophobic and thus provide additional protection to the ceramic particle 105 and prevent its erosion by water. Furthermore, the ZnO layer 140 also increases the hardness of the ceramic particle 105.

[0016] The ceramic particles 105 consist of at least one of the following materials: ceramic oxides, garnet-structured oxides, perovskite-structured oxides, or sulfides. The lithium-ion conductivity of the ceramic oxides is greater than 10 -5 cm 2 / s (diffusion coefficient).

[0017] The ceramic oxides represent LAGPs (lithium aluminum germanium phosphate) with NASICON structures (sodium superion conductors). The oxides with garnet structure can be LLZOs (Li7La3Zr2O). 12 The materials used are lithium lanthanum zirconia, the oxides with a perovskite structure are LLTOs (lithium lanthanum titanium oxide), and the sulfides are LPSCs (LPSCl, sulfide solid electrolyte). The ceramic particles 105 can be formed by combining the above-mentioned materials in any desired ratio.

[0018] The ceramic particles 105 consist of at least one of the following materials: LLZO (Li7La3Zr2O 12 ), Ga-LLZO (gallium-doped LLZO), Cu-LLZO (copper-doped LLZO), Ta-LLZO (tantalum-doped LLZO), Sr-LLZO (strontium-doped LLZO) or Al-LLZO (aluminium-doped LLZO).

[0019] If the ceramic particles 105 consist of LAGPs, the LAGPs are made of Li 1+x Al x Ge 2-x (PO4)3 or Li 1+x+y Al x Ge 2-x-y-z My N z (PO4)3 selected where 0.1≤x≤0.8, 0≤y≤0.2, 0≤z≤0.2, M a trivalent cation (such as scandium cation (Sc 3+ ), Yttrium cation (Y 3+ ), Gallium cation (Ga 3+ ), Indium cation (In 3+ ) or lanthanum cation (La 3+ )) and N a tetravalent cation (such as zirconium cation (Zr) 4+ ), silicon cation (Si 4+ ) or tin cation (Sn 4+ )) is.

[0020] In application, the dry electrode material 22 is solid at room temperature. Upon heating to a specific temperature (between 50°C and 240°C), a copolymer of PEOs, lithium salts 19, and CMCs melts, causing the dry electrode material 22 to become sticky. This allows the sticky dry electrode material 22 to adhere to the negative electrode substrate 21, thus forming the negative electrode plate.

[0021] In the prior art, the negative electrode substrate is coated with the negative electrode compound using a solvent (in this case, water). Drying and rolling steps are then performed, so that the negative electrode compound forms a negative electrode layer and adheres to the negative electrode substrate. According to the invention, the dry electrode compound material 22 melts at high temperatures and adheres to the negative electrode substrate 21 in its molten state. Drying and rolling steps are therefore eliminated. Since the dry electrode compound material 22 is a solid, the production of the negative electrode plate and the negative electrode substrate 21 cannot be carried out simultaneously.The dry electrode material 22 is readily available, can be stored at room temperature, and offers greater flexibility in the fabrication of the negative electrode plate, allowing the fabrication of the negative electrode plate and the dry electrode material 22 to be carried out separately. In the dry electrode material 22, the negative particles 15 serve as the active material for storing or releasing lithium ions. The polymer material 17 serves to disperse and support the material. The conductivity of the lithium ions in the polymer material 17 is low. Therefore, lithium salts 19 are added to the polymer material 17 to increase the lithium ion density. Under an electrical potential difference in the dry electrode material 22, the lithium ions can rapidly enter and exit, thus increasing the conductivity of the lithium ions.Since electrical conductivity is also important, conductivity agents 13 are added to the dry electrode mass material 22 to improve electrical conductivity.

[0022] A negative electrode plate with a dry electrode material containing ceramic particles with a NASICON structure, manufactured independently of a battery substrate, is used in a solid-state or semi-solid-state battery. The negative electrode plate consists of a negative electrode substrate and a layer of negative electrode material adhered to it. The dry electrode material contains several negative electrode particles, several polymer oxides (PEOs) for lithium ion guidance and to increase the lithium ion conductivity of the negative electrode. The PEOs are thermoplastic, meaning they melt at high temperatures and are present in a molten state, as well as several ceramic metal compounds (CMCs). The dry electrode material also contains several conductive agents, several lithium salts, and several auxiliary ceramic particles. Therefore, the production of the dry electrode material and the negative electrode substrate cannot be performed simultaneously.

[0023] In describing the invention, it is obvious that it can be modified in many ways. Such modifications do not constitute a departure from the spirit and scope of the invention, and all modifications obvious to a person skilled in the art fall within the scope of protection of the following claims.

Claims

[1] Negative electrode plate with dry electrode mass material containing NASICON structural ceramic particles and manufactured independently of the battery substrate; the negative electrode plate is used in a solid-state or semi-solid-state battery. The negative electrode plate includes: a negative electrode substrate that serves as a support material for the negative electrode; a negative electrode mass layer that adheres to the negative electrode substrate and forms the negative electrode plate; the negative electrode mass layer consists of the dry electrode mass material; The dry electrode mass material comprises: A multitude of negative electrode particles, which serve to store or release lithium ions, each of the negative electrodes representing an active material; Several PEOs (polyethylene oxides) serve to guide lithium ions and increase the lithium ion conductivity of the negative electrode. The PEOs are thermoplastic and therefore melt at high temperatures. Several CMCs (carboxymethylcelluloses) are formed from polymer materials. A copolymer formed from PEOs and CMCs is melted, resulting in a sticky dry electrode material. This sticky, dry electrode material adheres to the substrate of the negative electrode, thus forming the negative electrode plate. The dry electrode mass material also contains: Several conductive agents to increase the electrical conductivity of the dry electrode mass material; Several lithium salts are used to improve the electrochemical quality of the battery. The lithium salts facilitate the sliding of the polymer chains within the polymer material and increase the conductivity of the ions. a multitude of ceramic composite particles which serve to guide the lithium ions to dispersed lithium ion channels in order to prevent side reactions between the lithium ions and the dry electrode mass material due to abnormal deposition of lithium ions in the dry electrode mass material; and The negative electrode particles, the composite ceramic particles, the conductivity agents, and the lithium salts are dispersed in the polymer material of the dry electrode compound. The dry electrode compound and the negative electrode substrate can be produced simultaneously. The dry electrode compound melts at high temperatures and then adheres to the negative electrode substrate. Using the dry electrode compound eliminates the drying and rolling steps in the manufacturing process. The dry electrode compound is independent of the negative electrode substrate and can be applied separately. During production, the dry electrode compound is melted and then bonded to the negative electrode substrate at high temperature to form the negative electrode plate. [2] Negative electrode plate according to claim 1, wherein each of the composite ceramic particles comprises: A ceramic particle; a hydroxide ion layer (OH) - ), which surrounds the outer surface of the ceramic particle, thus forming a second composite particle; A dopamine layer surrounds the outer surface of the second composite particle, thus forming the composite ceramic particles. The hydroxide ion layer is formed by TRIS (tris(hydroxymethyl)aminomethane, (HOCH2)3CNH2), which is added during the production of the ceramic composite particles. [3] Negative electrode plate according to claim 2, wherein each TRIS molecule in the TRIS material has three OH groups - It has ions: namely, a first OH. - ion, a second OH - ion and a third OH - Ion. The first OH - ions and the second OH - Ions of the TRIS molecules are bound to the oxidizing functional groups of the corresponding ceramic particle via hydrogen bonds. The third OH -Ions from the TRIS molecules extend outwards to the outer surface of the corresponding ceramic particle, thus forming the hydroxide ion layer on the ceramic particle. The dopamine layer consists of a multitude of copolymerized dopamine molecules, where OH - Ions of dopamine molecules bind to the third OH group via dehydration condensation. - Ions of the TRIS molecules are bound, allowing the dopamine molecules to be combined with the second composite particle. [4] Negative electrode plate according to claim 2, wherein an outer surface of the corresponding dopamine layer of composite ceramic particles additionally encloses a ZnO (zinc oxide) layer; the ZnO layer consists of a plurality of ZnOs. [5] Negative electrode plate according to claim 4, wherein the ceramic particles consist of at least one of the following materials: ceramic oxides, garnet-structured oxides, perovskite-structured oxides or sulfides; and the lithium ion conductivity of the ceramic oxides is higher than 10 -5 cm 2 / s (diffusion coefficient) is. [6] Negative electrode plate according to claim 5, wherein the ceramic oxides are LAGPs (lithium aluminum germanium phosphate) with NASICON structures (sodium (Na) superion conductors). [7] Negative electrode plate according to claim 1, wherein the ceramic particles consist of LAGPs and the LAGPs are made of Li 1+x Al x Ge 2-x (PO4)3 or Li 1+x+y Al x Ge 2-x-y-z M y N z (PO4)3 are selected, where 0.1≤x≤0.8, 0≤y≤0.2, 0≤z≤0.2, M is a trivalent cation and N is a tetravalent cation. [8] Negative electrode plate according to claim 5, wherein the sulfides are LPSC (LPSCl, sulfide solid electrolyte). [9] Negative electrode plate according to claim 1, wherein the negative electrode particles consist of at least one of the following materials: carbon materials, Si-C composites or SiOx-C composites, wherein the carbon materials are selected from graphite, hard carbons and soft carbons. [10] Negative electrode plate according to claim 1, wherein the polymer material additionally contains at least one of several PVAs (polyvinyl alcohol) and SBRs (styrene-butadiene rubber). [11] Negative electrode plate according to claim 1, wherein the conductive means additionally contain sinapic acid as a dispersing agent. [12] Negative electrode plate according to claim 1, wherein the weight ratio of the negative electrode particles, the polymer and the lithium salts, the conductive means and the ceramic composite particles is between 90-95:8-4:2-1. [13] Negative electrode plate according to claim 1, wherein the conductive means are selected from at least one of carbon nanotubes, graphene and amorphous carbons. [14] Negative electrode plate according to claim 1, wherein the lithium salts are at least one of the following: PDDA-TFSI (poly(diallyldimethylammonium)-bis(trifluoromethanesulfonyl)imide) or Py14-TFSI. [15] Negative electrode plate according to claim 14, wherein the lithium salts are also at least one of the following: LiBOB, Li3PO4, LiFSI (lithium bis(fluorosulfonyl)imide), LiTFSI (LiN(CF3SO2)2 or LiPF6. [16] Negative electrode plate according to claim 7, wherein the trivalent cation is from scandium cation (Sc 3+ ), Yttrium cation (Y3+ ), Gallium cation (Ga 3+ ), Indium cation (In 3+ ) and lanthanum cation (La 3+ ) is selected and the tetravalent cation is from zirconium cation (Zr 4+ ), silicon cation (Si 4+ ) and tin cation (Sn 4+ ) is selected.

Images