Search

KR-20260067410-A - POSITIVE ELECTRODE SLURRY FOR ALL-SOLID-STATE BATTERY AND METHOD FOR PRODUCING SAME, ALL-SOLID-STATE BATTERY PRODUCED USING SAME

KR20260067410AKR 20260067410 AKR20260067410 AKR 20260067410AKR-20260067410-A

Abstract

The present invention relates to a positive electrode slurry for an all-solid-state battery, a method for manufacturing the same, and an all-solid-state battery manufactured using the same. More specifically, the invention comprises a positive electrode active material; a conductive material; a binder; a sulfide-based solid electrolyte; a phosphine-based additive represented by the above-described chemical formula 1; and a solvent.

Inventors

  • 오대양

Assignees

  • 삼성에스디아이 주식회사

Dates

Publication Date
20260513
Application Date
20241104

Claims (20)

  1. Cathode active material; Challenge material; bookbinder; Sulfide-based solid electrolyte; A phosphine-based additive represented by the following chemical formula 1; and containing a solvent Anode slurry for all-solid-state batteries: [Chemical Formula 1] In the above chemical formula 1, The above n 1 to n 3 are each independently 0 to 5, and The above R1 to R3 are each independently a hydrogen atom, a halogen group, a nitrile group, a nitro group, an amine group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted C5 to C14 heteroaryl group.
  2. In paragraph 1, The above phosphine-based additives are triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, and tris(4-methoxy-3,5-dimethylphenyl)phosphine. Comprising at least one selected from the group consisting of (Tris(4-methoxy-3,5-dimethylphenyl)phosphine), Tris(3,5-dimethylphenyl)phosphine, Tri(o-tolyl)phosphine, Diphenyl(p-tolyl)phosphine, or combinations thereof, Anode slurry for all-solid-state batteries.
  3. In paragraph 1, The content of the above phosphine-based additive is included in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the total of the above cathode active material, the above conductive material, and the above binder. Anode slurry for all-solid-state batteries.
  4. In paragraph 1, The content of the above sulfide-based solid electrolyte is 5 to 25 parts by weight based on 100 parts by weight of the total of the above positive active material, the above conductive material, and the above binder. Anode slurry for all-solid-state batteries.
  5. In paragraph 1, The content of the solvent comprises 15 to 50 parts by weight based on 100 parts by weight of the total anode active material, conductive material, and binder. Anode slurry for all-solid-state batteries.
  6. In paragraph 1, The weight ratio of the phosphine-based additive to the sulfide-based solid electrolyte is 0.2 to 25, Anode slurry for all-solid-state batteries.
  7. In paragraph 1, The above-mentioned positive electrode active material comprises a compound of the following chemical formula 2, Anode slurry for all-solid-state batteries: [Chemical Formula 2] Li a Ni x Co y Mn z X c O 2-b In the above chemical formula 2, 0.8≤a≤1.2, 0.8≤x≤1.0, 0≤y≤0.1, 0≤z≤0.1, 0≤c≤0.1, 0≤b≤0.05, and x + y + z + c = 1, and X is at least one element selected from the group consisting of Al, Ti, Mg, Zr, Mo and Nb.
  8. In paragraph 1, The above binder comprises a fluoride-based binder, Anode slurry for all-solid-state batteries.
  9. In paragraph 1, The above conductive material comprises at least one selected from the group consisting of natural graphite, artificial graphite, carbon black, acetylene black, ketjenblack, carbon fiber, carbon nanofiber, carbon nanotube, or a combination thereof. Anode slurry for all-solid-state batteries.
  10. In paragraph 1, The above sulfide-based solid electrolyte is an argyrodite-type compound comprising Li 7-a M a PS 6-c X c (0≤a≤2, 0≤c≤2), and The above X is F, Br, Cl, I, or a combination thereof, and The above M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof, Anode slurry for all-solid-state batteries.
  11. A mixture comprising a positive electrode active material, a conductive material, a binder, a sulfide-based solid electrolyte, a phosphine-based additive represented by the following chemical formula 1, and a solvent. Method for manufacturing a positive electrode slurry for all-solid-state batteries: [Chemical Formula 1] In the above chemical formula 1, The above n 1 to n 3 are each independently 0 to 5, and The above R1 to R3 are each independently a hydrogen atom, a halogen group, a nitrile group, a nitro group, an amine group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted C5 to C14 heteroaryl group.
  12. In Paragraph 11, The above phosphine-based additives are triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, and tris(4-methoxy-3,5-dimethylphenyl)phosphine. Comprising at least one selected from the group consisting of (Tris(4-methoxy-3,5-dimethylphenyl)phosphine), Tris(3,5-dimethylphenyl)phosphine, Tri(o-tolyl)phosphine, Diphenyl(p-tolyl)phosphine, or combinations thereof, Method for manufacturing a positive electrode slurry for an all-solid-state battery.
  13. In Paragraph 11, The above binder includes a fluoride-based binder, The above sulfide-based solid electrolyte is an argyrodite-type compound comprising Li 7-a M a PS 6-c X c (0≤a≤2, 0≤c≤2), and The above X is F, Br, Cl, I, or a combination thereof, and The above M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof, Method for manufacturing a positive electrode slurry for an all-solid-state battery.
  14. In Paragraph 11, The content of the above phosphine-based additive is included in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the total of the above cathode active material, the above conductive material, and the above binder. Method for manufacturing a positive electrode slurry for an all-solid-state battery.
  15. In Paragraph 11, The content of the above sulfide-based solid electrolyte is 5 to 25 parts by weight based on 100 parts by weight of the total of the above positive active material, the above conductive material, and the above binder. Method for manufacturing a positive electrode slurry for an all-solid-state battery.
  16. In Paragraph 11, The weight ratio of the phosphine-based additive to the sulfide-based solid electrolyte is 0.2 to 25, Method for manufacturing a positive electrode slurry for an all-solid-state battery.
  17. Anode; cathode; and a solid electrolyte layer between the anode and the cathode, comprising: The above positive electrode comprises a positive current collector and a positive active material layer on the positive current collector, and The above-mentioned positive active material layer is formed using a positive slurry according to any one of claims 1 to 10, All-solid-state battery.
  18. In Paragraph 17, The above positive electrode active material layer comprises a binder modifying material produced by reacting the leaching material of the above sulfide-based solid electrolyte with a phosphine-based additive, All-solid-state battery.
  19. In Paragraph 18, The binder modifying material comprises at least one selected from the group consisting of triphenylphosphine sulfide, phosphorous sulfide, lithium sulfide, or a combination thereof. All-solid-state battery.
  20. In Paragraph 18, The content of the binder modifying material in the above positive electrode active material layer is 0.0001 weight% to 1 weight%, All-solid-state battery.

Description

Positive electrode slurry for all-solid-state battery and method for producing the same, all-solid-state battery produced using the same The present invention relates to a positive electrode slurry for an all-solid-state battery, a method for manufacturing the same, and an all-solid-state battery manufactured using the same. Recently, driven by industrial demands, the development of batteries with high energy density and safety is actively underway. For example, lithium-ion batteries are being commercialized not only in the fields of information and communication devices but also in the automotive sector. In the automotive sector, safety is considered particularly important because it is directly related to human life. Recently, all-solid-state batteries in which liquid electrolytes are replaced with solid electrolytes have been proposed. By not using flammable organic dispersion media, all-solid-state batteries can significantly reduce the likelihood of fire or explosion in the event of a short circuit. Therefore, these all-solid-state batteries can offer significantly higher safety compared to lithium-ion batteries that use liquid electrolytes. FIG. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention. FIG. 2 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention. FIGS. 3 and FIGS. 4 are a plan view and a cross-sectional view, respectively, of an all-solid-state battery according to another embodiment of the present invention. FIG. 5 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention. FIG. 6 is a cross-sectional view of an all-solid-state battery including a gasket structure according to another embodiment of the present invention. FIG. 7 is an enlarged view illustrating a positive electrode active material layer according to embodiments of the present invention. FIGS. 8 and 9 are the results of evaluating the bending strength of the anode according to the examples and comparative examples. In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention are described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and various modifications can be made. The description of these embodiments is provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention. In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the components are exaggerated for the effective description of the technical content. Throughout the specification, parts indicated by the same reference numeral represent the same components. The embodiments described herein will be described with reference to cross-sectional and/or plan views, which are exemplary illustrations of the invention. In the drawings, the thicknesses of films and regions are exaggerated for effective description of the technical content. Accordingly, the regions illustrated in the drawings are schematic in nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific forms of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. The embodiments described and illustrated herein also include their complementary embodiments. The terms used herein are for describing the embodiments and are not intended to limit the invention. In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. As used herein, 'comprises' and/or 'comprising' do not exclude the presence or addition of one or more other components to the mentioned components. In this specification, "combination of these" may mean a mixture of components, a laminate, a composite, a copolymer, an alloy, a blend, and a reaction product, etc. Unless otherwise defined in this specification, the particle size may be the average particle size. Additionally, the particle size refers to the average particle size ( D50 ), which represents the diameter of a particle whose cumulative volume in the particle size distribution is 50% by volume. The average particle size ( D50 ) may be measured by methods widely known to those skilled in the art, for example, by measuring with a particle size analyzer, or by me