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EP-4738512-A1 - SOLID ELECTROLYTE, POSITIVE ELECTRODE INCLUDING THE SAME, AND METHOD OF MANUFACTURING THE SAME

EP4738512A1EP 4738512 A1EP4738512 A1EP 4738512A1EP-4738512-A1

Abstract

Disclosed are solid electrolytes, positive electrodes, and methods of manufacturing the solid electrolytes. The solid electrolyte includes a cluster that includes an active material particle and solid electrolyte particles. The solid electrolyte particles are in contact with the active material particle. Each of the solid electrolyte particles includes a linear carbon-based conductive material dispersed in the solid electrolyte particle. The active material particle of the cluster is electrically connected to a first solid electrolyte particle among the solid electrolyte particles. A second solid electrolyte particle among the solid electrolyte particles and the first solid electrolyte particle are in contact with each other to form an electrical path through the linear carbon-based conductive material of the first solid electrolyte particle and the linear carbon-based conductive material of the second solid electrolyte particle.

Inventors

  • KIM, HANSEUL
  • AN, SEONHYEOK
  • KIM, DONGSU

Assignees

  • SAMSUNG SDI CO., LTD.

Dates

Publication Date
20260506
Application Date
20251103

Claims (15)

  1. A positive electrode (100) for an all-solid-state battery (10), the positive electrode (100) comprising: a cluster (CLU) that comprises an active material particle (CAC) and a plurality of solid electrolyte particles (SEP), wherein the plurality of solid electrolyte particles (SEP) are in contact with the active material particle (CAC), wherein at least one of the plurality of solid electrolyte particles (SEP) comprises a linear carbon-based conductive material (CDM) dispersed in the solid electrolyte particle, wherein the active material particle (CAC) of the cluster (CLU) is electrically connected to a first solid electrolyte particle (SEP1) among the plurality of solid electrolyte particles (SEP), and wherein a second solid electrolyte particle (SEP2) among the plurality of solid electrolyte particles (SEP) and the first solid electrolyte particle (SEP1) are in contact with each other to form an electrical path (ETP) through the linear carbon-based conductive material (CDM) of the first solid electrolyte particle (SEP1) and the linear carbon-based conductive material (CDM) of the second solid electrolyte particle (SEP2).
  2. The positive electrode (100) of claim 1, wherein at least one of the plurality of solid electrolyte particles (SEP) comprises: a matrix (EM) comprising a sulfide-based solid electrolyte; and the linear carbon-based conductive material (CDM) in the matrix (EM).
  3. The positive electrode (100) of claim 1 or 2, wherein at least one of the plurality of solid electrolyte particles (SEP) comprises: a matrix (EM) comprising a sulfide-based solid electrolyte, wherein the sulfide-based solid electrolyte comprises an argyrodite-type sulfide-based solid electrolyte represented by Li 7-a-c M a PS 6-c X c (where 0 ≤ a ≤ 2 and 0 ≤ c ≤ 2), wherein X comprises at least one of F, Br, and Cl, and wherein M comprises at least one of scandium (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), and bismuth (Bi).
  4. The positive electrode (100) according to any one of claims 1 to 3, wherein the linear carbon-based conductive material (CDM) comprises at least one of carbon nanotube (CNT), carbon nanofiber (CNF), and vapor-grown carbon fiber (VGCF).
  5. The positive electrode (100) according to any one of claims 1 to 4, wherein an average particle diameter of each of the plurality of solid electrolyte particles (SEP) is in a range of ≥ 0.5 µm to ≤ 2 µm.
  6. An all-solid-state battery (10), comprising: a positive electrode (100) that comprises a positive electrode current collector (110), and a positive electrode active material layer (120) on the positive electrode current collector (110); a solid electrolyte layer (300); and a negative electrode (200), wherein the positive electrode active material layer (120) comprises a positive electrode active material particle (CAC) and a first solid electrolyte particle (SEP1), wherein the first solid electrolyte particle (SEP1) comprises a linear carbon-based conductive material (CDM) dispersed in the first solid electrolyte particle (SEP1), and wherein the linear carbon-based conductive material (CDM) is configured to penetrate the first solid electrolyte particle (SEP1) to form an electrical path (ETP) between a first location (LO1) and a second location (LO2) on a surface of the first solid electrolyte particle (SEP1).
  7. The all-solid-state battery (10) of claim 6, wherein a thickness of the positive electrode active material layer (120) is in a range of ≥ 100 µm to ≤ 1,000 µm.
  8. The all-solid-state battery (10) of claim 6 or 7, wherein the solid electrolyte layer (300) comprises a second solid electrolyte particle (SEP2), wherein the second solid electrolyte particle (SEP2) excludes the linear carbon-based conductive material (CDM).
  9. The all-solid-state battery (10) according to any one of claims 6 to 8, wherein the solid electrolyte layer (300) comprises a second solid electrolyte particle (SEP2), and wherein an average particle diameter of the first solid electrolyte particle (SEP1) is less than an average particle diameter of the second solid electrolyte particle (SEP2).
  10. The all-solid-state battery (10) according to any one of claims 6 to 9, wherein an amount of the first solid electrolyte particle (SEP1) is in a range of ≥ 10 wt% to ≤ 30 wt% of a total weight of the positive electrode active material layer (120).
  11. A method of manufacturing a solid electrolyte, the method comprising: mixing an electrolyte precursor and a linear carbon-based conductive material (CDM) to obtain a mixture; and thermally treating the mixture to prepare a solid electrolyte particle (SEP), wherein the linear carbon-based conductive material (CDM) is configured to penetrate the solid electrolyte particle (SEP) to form an electrical path (ETP) between a first location (LO1) and a second location (LO2) on a surface of the solid electrolyte particle (SEP).
  12. The method of claim 11, wherein mixing the electrolyte precursor and the linear carbon-based conductive material (CDM) is performed via a ball milling process.
  13. The method of claim 11 or 12, wherein the electrolyte precursor comprises at least one of a sulfur precursor, a phosphorus precursor, and a halide precursor.
  14. The method according to any one of claims 11 to 13, wherein thermally treating the mixture is performed at a temperature in a range of ≥ 100°C to ≤ 800°C.
  15. The method according to any one of claims 11 to 14, wherein an amount of the linear carbon-based conductive material (CDM) is in a range of ≥ 1 wt% to ≤ 5 wt% relative to a total weight of the mixture.

Description

CROSS-REFERENCE TO RELATED APPLICATION This application claims priority under 35 U.S.C 119 to Korean Patent Application No. 10-2024-0155280 filed on November 5, 2024 in the Korean Intellectual Property Office, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND Examples of the present disclosure relate to an all-solid-state battery. There is increasing development of high-energy density and safe batteries driven by industrial demands. For example, lithium ion batteries are commercialized not only in formation-related and communication devices, but also in the automotive industry. In the automotive industry, safety is emphasized due to its direct relation to the safety of human lives. An all-solid-state battery typically includes a solid electrolyte in place of a liquid electrolyte. As an all-solid-state battery does not use a flammable organic dispersion medium, the possibility of fire or explosion may be significantly reduced, even in the event of short-circuit. Therefore, an all-solid-state battery may have high stability. SUMMARY An example embodiment of the present disclosure provides a solid electrolyte in which a conductive material is dispersed inside a particle to improve electronic conductivity and ionic conductivity of a positive electrode. An example embodiment of the present disclosure provides a positive electrode in which particles are uniformly mixed to improve electrode performance. According to an example embodiment of the present disclosure, a positive electrode for an all-solid-state battery may include a cluster that includes an active material particle and a plurality of solid electrolyte particles. The plurality of solid electrolyte particles may be in contact with the active material particle. Each of the plurality of solid electrolyte particles may include a linear carbon-based conductive material dispersed in the solid electrolyte particle. The active material particle of the cluster may be electrically connected to a first solid electrolyte particle among the plurality of solid electrolyte particles. A second solid electrolyte particle among the plurality of solid electrolyte particles and the first solid electrolyte particle may be in contact with each other to form an electrical path through the linear carbon-based conductive material of the first solid electrolyte particle and the linear carbon-based conductive material of the second solid electrolyte particle. According to an example embodiment of the present disclosure, an all-solid-state battery may include a positive electrode that includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector; a solid electrolyte layer; and a negative electrode. The positive electrode active material layer may include a positive electrode active material particle and a first solid electrolyte particle. The first solid electrolyte particle may include a linear carbon-based conductive material dispersed in the first solid electrolyte particle. The linear carbon-based conductive material may be configured to penetrate the first solid electrolyte particle to form an electrical path between a first location and a second location on a surface of the first solid electrolyte particle. According to an example embodiment of the present disclosure, a method of manufacturing a solid electrolyte may include mixing an electrolyte precursor and a linear carbon-based conductive material to obtain a mixture; and thermally treating the mixture to prepare a solid electrolyte particle. The linear carbon-based conductive material may be configured to penetrate the solid electrolyte particle to form an electrical path between a first location and a second location on a surface of the solid electrolyte particle. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 illustrates a plan view showing an all-solid-state battery, according to an example embodiment of the present disclosure.FIG. 2 illustrates a cross-sectional view taken along line A-A' of FIG. 1.FIG. 3 illustrates an enlarged cross-sectional view of section "M" depicted in FIG. 2, showing a positive electrode active material layer according to an example embodiment of the present disclosure.FIG. 4 illustrates a diagram showing a cluster according to an example embodiment of the present disclosure.FIG. 5 illustrates a diagram showing a solid electrolyte particle according to an example embodiment of the present disclosure.FIG. 6 illustrates an enlarged view showing a positive electrode active material layer according to an example embodiment of the present disclosure.FIG. 7 illustrates a cross-sectional view showing an all-solid-state battery according to an example embodiment of the present disclosure.FIG. 8 illustrates a cross-sectional view showing an all-solid-state battery according to an example embodiment of the present disclosure.FIG. 9 illustrates a cross-sectional view showing an all-solid-state bat