Positive electrode mass with dry electrode mass material, which is produced independently of the battery substrate.

Abstract

Positive electrode plate with dry electrode material, which is manufactured independently of the substrate of a battery; the positive electrode plate is used in a solid-state or semi-solid-state battery; the positive electrode plate includes: a positive electrode substrate, which serves as a support material for the positive electrode; a positive electrode mass layer which adheres to the positive electrode substrate and thus forms the positive electrode plate; the positive electrode mass layer consists of the dry electrode mass material; The dry electrode mass material comprises: A multitude of positive electrode particles for storing or releasing lithium ions, each of the positive electrode particles being an active material; A variety of PEOs (polyethylene oxide) for conducting lithium ions and increasing the conductivity of the positive electrode; the PEOs are thermoplastic, meaning they melt at high temperatures and are already in a molten state; a variety of PVDFs (polyvinylidene fluoride) or PVDF-HFPs (vinylidene fluoride-co-hexafluoropropylene), which are polymer materials; wherein a copolymer of the PEOs and the PVDF-HFP or PVDF is already melted, so that the dry electrode mass material is sticky; the sticky dry electrode mass material adheres to the positive electrode substrate and thus forms the positive electrode plate. The dry electrode mass material also includes: a variety of conductive agents to increase the electrical conductivity of the dry electrode mass material; Several lithium salts serve to improve the electrochemical quality of the battery; the lithium salts facilitate the sliding of the polymer chains of the polymer material and increase the conductivity of the ions; Several ceramic particles 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 wherein the positive electrode particles, the ceramic particles, the conductivity agents, and the lithium salts are dispersed in the polymer material of the dry electrode mass material; the production of the dry electrode mass material and the production of the positive electrode substrate do not have to be simultaneous; the dry electrode mass material melts at high temperatures and then adheres to the positive electrode substrate; and by using the dry electrode mass material, the drying and rolling steps in the manufacturing process are avoided; the dry electrode mass material is independent of the positive electrode substrate and can be transported separately; in the manufacturing process, the dry electrode mass material is melted and then allowed to adhere to the positive electrode substrate at high temperature to form the positive electrode plate.

Description

FIELD OF INVENTION

[0001] The invention relates to an electrode plate, in particular a positive electrode plate made of dry electrode mass material, which is produced independently of a battery substrate. BACKGROUND OF THE INVENTION

[0002] According to the current state of the art, a positive electrode consists of a positive electrode substrate and a layer of positive electrode material applied to it. The positive electrode material layer is formed exclusively by positive electrode material. This positive electrode material comprises several positive electrode particles capable of storing or releasing lithium ions, several polymers including PVDF (polyvinylidene fluoride), a solvent for dispersing the positive electrode material, several conductive agents to increase electrical conductivity, and several ceramic particles for guiding 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 positive electrode compound to ensure uniform distribution of the material. The positive electrode compound, along with the solvent, is then applied to the positive electrode substrate and subsequently dried to remove the solvent. Evaporation of the solvent creates holes in the positive electrode layer, necessitating a rolling step. This ensures a strong bond between the positive electrode compound layer and the positive electrode substrate.

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

[0005] The invention therefore aims to solve this problem of 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 positive electrode plate made of dry electrode material, which is produced independently of the battery substrate. The PEOs are thermoplastic, melt at high temperatures, and subsequently adhere to the positive electrode substrate. The use of thermoplastic PEOs eliminates drying and rolling steps for removing the solvent from the positive electrode material. This eliminates the drying step and prevents material breakage during rolling. Furthermore, this manufacturing method extends the shelf life of the positive electrode plate. BRIEF DESCRIPTION OF THE IMAGES Fig. shows a schematic view illustrating the structure of the invention. Fig. Figure 1 shows a cross-sectional view illustrating the structure of the composite ceramic particle according to the invention. DETAILED DESCRIPTION OF THE INVENTION

[0007] The invention relates to a positive electrode plate with dry electrode material, which is produced independently of the battery substrate. A solid-state or semi-solid battery comprises a positive electrode 20. This positive electrode 20 consists of the following elements: A positive electrode substrate 21 serves as a support material for the positive electrode 20. The positive electrode substrate 21 is designed as an aluminum foil. A positive electrode material layer 23 is applied to the positive electrode substrate 21, thus forming a positive electrode plate. According to the invention, the positive electrode material layer 23 consists of the dry electrode material 22. The dry electrode material 22 is formed independently of the positive electrode substrate 21 and can be applied separately. In application, the dry electrode material 22 is melted and then applied to the positive electrode substrate 21 at a high temperature.

[0008] The dry electrode mass material 22 comprises the following elements: A multitude of positive electrode particles 15 serve to store or release lithium ions. The positive electrode particles 15 are selected from LCO particles (LiCoO2), single-crystal NCM particles (lithium nickel manganese cobalt oxide), polycrystalline NCM particles, LMFP particles (lithium manganese iron phosphate), LFP particles (LiFePO4), etc., but preferably from NCM811 or NCMN9. Each of the positive electrode particles 15 constitutes an active material. The weight fraction of the positive electrode particles 15 in the dry electrode mass material 22 is between 88 and 97 wt.%, where wt.% means the weight fraction. A variety of PEOs (polyethylene oxides) serve as lithium ion carriers and increase the lithium ion conductivity of the positive electrode. The PEOs are thermoplastic, meaning they melt at high temperatures and are therefore in a molten state. The polymer material 17 consists of several PVDFs (polyvinylidene fluoride) or PVDF-HFPs (vinylidene fluoride-co-hexafluoropropylene). Thanks to the thermoplastic properties of the PEOs, the dry electrode material 22 can be melted and then adhered to the positive electrode substrate 21 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. This reduces manufacturing costs and prevents material fractures in the positive electrode layer 23 caused by rolling. As a result, the shelf life of the positive electrode plate is extended. The polymer material 17 also contains at least one of several PVAs (polyvinyl alcohol) and several HDPEs (high-density polyethylene). PVAs and PEOs are compatible. PVAs and PEOs reduce the risk of crystallization of the dry electrode mass material 22, ensuring firm adhesion to the positive electrode substrate 21. HDPEs exhibit high toughness and thus contribute to the strength and toughness of the positive electrode plate. PEOs are thermoplastic, meaning they melt at high temperatures and then adhere to the positive electrode substrate 21. The thermoplastic nature of the PEOs eliminates drying and rolling steps in the manufacturing process and prevents the material from breaking in the positive electrode mass layer 23 during rolling. The dry electrode mass material 22 also contains: Several conductive materials 13, selected from at least one of the following: carbon nanotubes, graphene, and amorphous carbon, wherein the amorphous carbon is, for example, Super P. The conductive materials 13 increase the electrical conductivity of the dry electrode mass material 22. Several lithium salts 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 materials: LiBOB, Li3PO4, LiFSI (Lithium Bis(fluorosulfonyl)imide), LiTFSI(CF3SO2)2 and 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 leads to a higher voltage difference in the lithium salt 19. This makes the polymer material 17 in the positive electrode more stable. Several ceramic particles 100 conduct the lithium ions to distributed lithium ion channels, thus preventing side reactions between the lithium ions and the dry electrode mass 22 due to abnormal deposition of the lithium ions in the dry electrode mass. 22. Referring to Fig. are the positive electrode particles 15, which ceramic particles 100, the conductivity agents 13 and the lithium salts 19 are dispersed in the polymer material 17 of the dry electrode mass material 22.

[0009] The weight ratio of the positive electrode particles 15, the polymer 17, the lithium salts 19, the conductive substances 13, and the ceramic particles 100 is between 88 and 97:10:2:1. The ratio of the positive electrode particles 15, the polymer 17, the lithium salts 19, the conductive substances 13, and the ceramic particles 100 is A:B:C. Here, A is in the range of 88 to 97, B is in the range of 10:2, and C is 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.

[0010] With reference to the Fig. A composite layer 110 surrounds the outer surface of each ceramic particle 100. The composite layer 110 comprises the following elements: A dopamine layer 120 surrounds the outer surface of the ceramic particle 100 and forms a second composite particle 140. The dopamine layer 120 consists of several copolymerized dopamine molecules. A PVDF layer 130 encloses the outer surface of the second composite particle 140. The PVDF layer 130 and the corresponding second composite particle 140 form a conductive composite particle 150. The PVDF layer 130 consists of several PVDF materials. The PVDF material of the PVDF layer 130 is not the PVDF in the dry electrode mass material 22, but rather an additional layer that encloses the second composite particle 140.

[0011] The dopamine layer 120 does not completely enclose the outer surface of the ceramic particle 100, leaving some parts of the outer surface of the ceramic particle 100 exposed. Consequently, some parts of the PVDF layer 130 contact the surface of the ceramic particle 100, while other parts of the PVDF layer 130 contact the dopamine layer 120.

[0012] Some parts of the fluoride ions (F - ) in the PVDFs of PVDF layer 130 are bound by ionic bonding with the lithium ions (Li + ) are bound to the outside of the ceramic particle 100, thus forming lithium fluoride (LiF). Another portion of the fluoride ions (F - ) in the PVDFs of the PVDF layer 130 is connected via hydrogen bonds to nitrogen ions on the copolymerized dopamine molecules of the surface of the second composite particle 140, so that the PVDF material forms the PVDF layer 130 and subsequently surrounds the outside of the second composite particle 140.

[0013] The ceramic particles 100 consist of at least one of the following materials: ceramic oxides, garnet-structured oxides, perovskite-structured oxides, and sulfides. The lithium ion conductivity of the ceramic oxides is greater than 10⁻⁵ cm² / s (diffusion coefficient).

[0014] The ceramic oxides are LAGPs (lithium aluminum germanium phosphate) with NASICON structures (sodium superion conductors). The oxides with garnet structures can be LLZOs (Li7La3Zr2O). 12 The materials used are lithium lanthanum zirconium oxide, the oxides with perovskite structures are LLTOs (lithium lanthanum titanium oxide), and the sulfides are LPSCs (LPSCl, sulfide solid electrolyte). The ceramic particles 100 can be formed by combining the above-mentioned materials in any desired ratio.

[0015] The ceramic particles 100 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) and Al-LLZO (Aluminium-doped LLZO).

[0016] If the ceramic particles consist of 100 LAGPs, the LAGPs will be 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 selected where 0.1≤x≤0.8, 0≤y≤0.2, 0≤z≤0.2, M is a trivalent cation (such as scandium cation (Sc3+), yttrium cation (Y3+), gallium cation (Ga3+), indium cation (In3+) or lanthanum cation (La3+)) and N is a tetravalent cation (such as zirconium cation (Zr4+), silicon cation (Si4+) or tin cation (Sn4+)).

[0017] In application, the dry electrode slurry material 22 is solid at room temperature. Upon heating to a specific temperature (between 50 °C and 240 °C), a copolymer of PEO, lithium salts 19, and PVDF-HFP or PVDF melts, causing the dry electrode slurry material 22 to become sticky. This allows the sticky dry electrode slurry material 22 to adhere to the positive electrode substrate 21, thus forming the positive electrode plate.

[0018] In the prior art, the positive electrode substrate is coated with solvent using the positive electrode compound. Drying and rolling steps are then carried out so that the positive electrode slurry forms a positive electrode layer and adheres to the positive electrode substrate. According to the invention, the dry electrode slurry material 22 melts at high temperatures and adheres to the positive electrode substrate 21 in its molten state. Drying and rolling steps are therefore eliminated. Since the dry electrode slurry material 22 is a solid, the production of the positive electrode plate and the positive electrode substrate 21 cannot be carried out simultaneously. The dry electrode slurry material 22 is readily available, can be stored at room temperature, and offers greater flexibility in the production of the positive electrode plate.The production of the positive electrode plate and the production of the dry electrode slurry material 22 are separable. In the dry electrode slurry material 22, the positive particles 15 serve as the active material for storing or releasing lithium ions. The polymer material 17 serves as a dispersion and carrier for the dry electrode slurry material 22. Since the conductivity of the lithium ions in the polymer material 17 is low, lithium salts 19 are added to the polymer material 17 to increase the lithium ion density. With an electrical potential difference in the dry electrode slurry material 22, the lithium ions can enter and exit rapidly, thus increasing the conductivity of the lithium ions. Since electrical conductivity is also important, conductive agents 13 are added to the dry electrode slurry material 22 to improve its electrical conductivity.

[0019] The invention relates to a positive electrode plate made of dry electrode material, which is produced independently of the battery substrate and is used in a solid-state or semi-solid-state battery. The positive electrode plate consists of a positive electrode substrate and a layer of the positive electrode material adhering to it. The dry electrode material contains several positive electrode particles and several PEOs for lithium ion guidance and for increasing the lithium ion conductivity of the positive electrode. PEOs are thermoplastic, meaning they melt at high temperatures and exist in the molten state as a multitude of PVDFs or PVDF-HFPs. The dry electrode material also contains several conductive agents, several lithium salts, and several ceramic particles as additives. Therefore, the production of the dry electrode material and the positive electrode substrate cannot be carried out simultaneously.

[0020] The invention is hereby described; it is obvious that it can be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all modifications obvious to a person skilled in the art are to fall within the scope of the following claim.

Claims

[1] Positive electrode plate with dry electrode mass material, which is manufactured independently of the substrate of a battery; the positive electrode plate is used in a solid-state or semi-solid-state battery; the positive electrode plate includes: a positive electrode substrate, which serves as a support material for the positive electrode; a positive electrode mass layer which adheres to the positive electrode substrate and thus forms the positive electrode plate; the positive electrode mass layer consists of the dry electrode mass material; The dry electrode mass material comprises: A multitude of positive electrode particles for storing or releasing lithium ions, each of the positive electrode particles being an active material; A variety of PEOs (polyethylene oxide) for conducting lithium ions and increasing the conductivity of the positive electrode; the PEOs are thermoplastic, meaning they melt at high temperatures and are already in a molten state; a variety of PVDFs (polyvinylidene fluoride) or PVDF-HFPs (vinylidene fluoride-co-hexafluoropropylene), which are polymer materials; wherein a copolymer of the PEOs and the PVDF-HFP or PVDF is already melted, so that the dry electrode mass material is sticky; the sticky dry electrode mass material adheres to the positive electrode substrate and thus forms the positive electrode plate. The dry electrode mass material also includes: a variety of conductive agents to increase the electrical conductivity of the dry electrode mass material; Several lithium salts serve to improve the electrochemical quality of the battery; the lithium salts facilitate the sliding of the polymer chains of the polymer material and increase the conductivity of the ions; Several ceramic particles 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 wherein the positive electrode particles, the ceramic particles, the conductivity agents, and the lithium salts are dispersed in the polymer material of the dry electrode mass material; the production of the dry electrode mass material and the production of the positive electrode substrate do not have to be simultaneous; the dry electrode mass material melts at high temperatures and then adheres to the positive electrode substrate; and by using the dry electrode mass material, the drying and rolling steps in the manufacturing process are avoided; the dry electrode mass material is independent of the positive electrode substrate and can be transported separately; in the manufacturing process, the dry electrode mass material is melted and then allowed to adhere to the positive electrode substrate at high temperature to form the positive electrode plate. [2] Positive electrode plate according to claim 1, wherein a composite layer encloses an outer surface of each of the ceramic particles; The composite layer comprises: A dopamine layer that surrounds the outer surface of the ceramic particle, thus forming a second composite particle, wherein the dopamine layer consists of several copolymerized dopamine molecules; a PVDF layer enclosing the outer surface of the second composite particle, wherein the PVDF layer and the corresponding second composite particle are formed as a single conductive composite particle; the PVDF layer consists of several PVDF materials; the PVDF material of the PVDF layer is not the PVDF in the dry electrode mass material, but a further layer enclosing the second composite particle; wherein the dopamine layer does not completely enclose the outer surface of the ceramic particle, so that some parts of the outer surface of the ceramic particle are exposed; as a result, some parts of the PVDF layer contact the surface of the ceramic particle and other parts of the PVDF layer contact the dopamine layer; and where some parts of the fluoride ions (F - ) in the PVDFs of the PVDF layer by ionic bonding with the lithium ions (Li + ) are bound to the outside of the ceramic particle, thus forming lithium fluoride (LiF); other parts of the fluoride ions (F - ) in the PVDFs of the PVDF layer are linked via hydrogen bonds to nitrogen ions on the copolymerized dopamine molecules of the surface of the second composite particle, so that the PVDF material forms the PVDF layer and subsequently surrounds the outside of the second composite particle. [3] Positive electrode plate according to claim 2, 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). [4] Positive electrode plate according to claim 3, wherein the ceramic oxides are LAGPs (lithium aluminum germanium phosphate) with NASICON structures (sodium (Na) superionic conductor). [5] Positive 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. [6] Positive electrode plate according to claim 5, wherein the trivalent cation is from scandium cation (Sc 3+ ), Yttrium cation (Y 3+ ), 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. [7] Positive electrode plate according to claim 3, wherein the oxides with garnet structures LLZOs (Li7La3Zr2O 12 , lithium lanthanum zirconium oxide) and the oxides with perovskite structures LLTOs (lithium lanthanum titanium oxide). [8] Positive electrode plate according to claim 1, wherein the ceramic particles 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) and Al-LLZO (aluminium-doped LLZO). [9] Positive electrode plate according to claim 3, wherein the sulfides are LPSC (LPSCl, sulfide solid electrolyte). [10] Positive electrode plate according to claim 1, wherein the positive electrode particles are selected from LCO particles (LiCoO2), single-crystal NCM particles (lithium nickel manganese cobalt oxide), polycrystalline NCM particles, LMFP particles (lithium manganese iron phosphate) or LFP particles (LiFePO4). [11] Positive electrode plate according to claim 1, wherein the weight ratio of the positive electrode particles, the polymer and the lithium salts, as well as the conductive materials and the ceramic particles, is between 88-97:10-2:2-1. [12] Positive electrode plate according to claim 1, wherein the polymer material additionally contains at least one of several PVAs (polyvinyl alcohol) and several HDPEs (high-density polyethylene). [13] Positive electrode plate according to claim 1, wherein the conductive materials are selected from at least one of several carbon nanotubes, graphene and amorphous carbons. [14] Positive electrode plate according to claim 1, wherein the lithium salts are selected from at least one of the following materials: PDDA-TFSI (poly(diallyldimethylammonium)-bis(trifluoromethanesulfonyl)imide) or Py14-TFSI. [15] Positive electrode plate according to claim 14, wherein the lithium salts also contain at least one of the following materials: LiBOB, Li3PO4, LiFSI (lithium bis(fluorosulfonyl)imide), LiTFSI (LiN(CF3SO2)2 and LiPF6.

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