KR-102963309-B1 - SOLID ELECTROLYTE MEMBRANE, PREPARATION METHOD THEREOF, AND ALL SOLID RECHARGEABLE BATTERIES

Abstract

The present invention relates to a solid electrolyte membrane comprising a composite and a solid electrolyte, wherein the composite comprises a core containing diamagnetic particles; an insulating layer surrounding the core; and a shell surrounding the insulating layer containing a solid electrolyte, a method for manufacturing the same, and an all-solid-state secondary battery.

Inventors

• 정미정
• 안선혁
• 오승현

Assignees

• 삼성에스디아이 주식회사

Dates

Publication Date

20260508

Application Date

20230830

Claims (20)

1. It includes a complex and a first solid electrolyte, The above complex is A core containing diamagnetic particles, An insulating layer surrounding the above core, and A solid electrolyte membrane comprising a shell containing a second solid electrolyte surrounding the insulating layer.
2. In Article 1, The above core is a solid electrolyte membrane with an aspect ratio greater than 1, represented by the following mathematical formula 1: [Mathematical Formula 1] Aspect ratio = Length of major axis / Length of minor axis.
3. In Article 2, A solid electrolyte membrane in which the major axis of the core is oriented in the range of 50° to 130° with respect to the plane direction of the solid electrolyte membrane.
4. In Article 1, The above core is a solid electrolyte membrane that is needle-shaped, plate-shaped, or elliptical.
5. In Article 1, The above diamagnetic particles comprise a carbon-based material, and the carbon-based material comprises a solid electrolyte membrane including artificial graphite, natural graphite, graphene, carbon nanotubes (CNT), L-carbon nanotubes (Long length CNT), carbon fibers, carbon black, or a combination thereof.
6. In Article 1, The above insulating layer comprises a polymer, and the polymer comprises a solid electrolyte membrane including polyethylene oxide, hydrogenated nitrile rubber, styrene-butadiene rubber, polyvinylidene fluoride, or a combination thereof.
7. In Article 1, A solid electrolyte membrane in which the weight ratio of the core and the insulating layer is 1:0.01 to 1:50.
8. In Article 1, The second solid electrolyte is a solid electrolyte membrane comprising a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or a combination thereof.
9. In Article 1, A solid electrolyte membrane in which the weight ratio of the core and the shell is 1:1 to 1:500.
10. In Article 1, The length of the major axis of the above core is 1 μm to 50 μm, and A solid electrolyte membrane having a short axis length of 0.01 μm to 5 μm of the above core.
11. In Article 1, A solid electrolyte membrane comprising 0.1% to 5% by weight of the composite with respect to 100% by weight of the solid electrolyte membrane.
12. In Article 1, The first solid electrolyte comprises a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or a combination thereof, and is in the form of particles with an average particle size (D 50 ) of 0.1 μm to 5.0 μm.
13. A composite is obtained comprising a core containing diamagnetic particles, an insulating layer surrounding the core, and a shell surrounding the insulating layer containing a second solid electrolyte. A slurry for forming an electrolyte membrane comprising the above composite and a first solid electrolyte is prepared, and A method for manufacturing a solid electrolyte membrane comprising applying the electrolyte membrane forming slurry onto a substrate.
14. In Article 13, A method for manufacturing a solid electrolyte membrane, further comprising applying a magnetic field to a slurry for forming an electrolyte membrane coated on a substrate.
15. In Article 14, The strength of the magnetic field is 0.1 T to 3 T, and A method for manufacturing a solid electrolyte membrane in which the application time of the magnetic field is 0.1 seconds to 10 minutes.
16. In Article 14, A method for manufacturing a solid electrolyte membrane, further comprising drying a slurry for forming an electrolyte membrane to which a magnetic field is applied to form a solid electrolyte membrane.
17. In Article 13, The above complex is After mixing the diamagnetic particles and the insulating material in the first solvent, the first drying is performed, and The product of the first drying and the second solid electrolyte raw material are mixed in a second solvent and then dried a second time, A method for manufacturing a solid electrolyte membrane obtained by heat treating the product of the second drying step.
18. In Article 17, A method for manufacturing a solid electrolyte membrane, wherein the preparation of the above electrolyte membrane forming slurry is to prepare a slurry by mixing the above composite, the first solid electrolyte, and the third solvent.
19. In Article 17, A method for manufacturing a solid electrolyte membrane in which the first drying is performed at 80°C to 150°C.
20. In Article 17, A method for manufacturing a solid electrolyte membrane in which the second drying is performed at 80°C to 150°C.

Description

Solid Electrolyte Membrane, Preparation Method Thereof, and All Solid Rechargeable Batteries The invention relates to a solid electrolyte membrane, a method for manufacturing the same, and an all-solid-state secondary battery including 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. Currently commercially available lithium-ion batteries use an electrolyte, and since the electrolyte contains a flammable organic dispersion medium, there is a possibility of overheating and fire if a short circuit occurs inside the battery. Accordingly, all-solid-state secondary batteries using a solid electrolyte instead of an electrolyte are being proposed. FIGS. 1 and FIGS. 2 are cross-sectional views schematically showing a composite (1) according to one embodiment. FIG. 3 is a schematic diagram showing a solid electrolyte membrane (300) according to one embodiment. FIG. 4 is a schematic perspective view of a solid electrolyte membrane (300) according to one embodiment. FIG. 5 is a schematic cross-sectional view of a solid electrolyte membrane (300) according to one embodiment. FIGS. 6 and FIGS. 7 are cross-sectional views schematically showing an all-solid-state secondary battery (100) according to one embodiment. Specific embodiments are described below in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. The terms used herein are for describing exemplary embodiments only and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. "Combinations of these" refers to mixtures of components, laminates, composites, copolymers, alloys, blends, reaction products, etc. Terms such as "include," "equip," or "have" are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not excluding in advance the existence or addition of one or more other features, numbers, steps, components, or combinations thereof. In the drawings, thicknesses have been enlarged to clearly represent various layers and regions, and the same reference numerals have been used for similar parts throughout the specification. When a part such as a layer, film, region, or plate is described as being "on" or "on" another part, this includes not only cases where it is "immediately on" another part, but also cases where there is another part in between. Conversely, when a part is described as being "immediately on" another part, it means that there is no other part in between. “Layers” include not only shapes formed on the entire surface when viewed in a plan view, but also shapes formed on some surfaces. “Particle size” or “average particle size” may be measured by methods widely known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with transmission electron microscope images or scanning electron microscope images. Alternatively, the average particle size value may be obtained by measuring using dynamic light scattering and performing data analysis to count the number of particles for each particle size range and then calculating from thereon. Unless otherwise defined, the average particle size may refer to the diameter (D 50 ) of a particle whose cumulative volume is 50% of the particle size distribution. Additionally, unless otherwise defined, the average particle size may be obtained by measuring the size (diameter or length of the major axis) of about 20 randomly selected particles from a scanning electron microscope image to obtain a particle size distribution, and taking the diameter (D 50 ) of the particle whose cumulative volume is 50% of the particle size distribution as the average particle size. “Thickness” may be measured, for example, through photographs taken with an electron microscope such as a scanning electron microscope. “Or” is not interpreted in an exclusive sense; for example, “A or B” is interpreted to include A, B, A+B, etc. The term “metal” is interpreted as a concept that includes ordinary metals, transition metals, and metalloids (semimetals). solid electrolyte membrane In one embodiment, a solid electrolyte membrane is provided comprising a composite and a solid electrolyte, wherein the composite comprises a core containing diamagnetic particles; an insulating layer surrounding the core; and a shell surrounding the insulating layer and containing a solid electrolyte. FIGS. 1 and 2 are schematic cross-sectional views of a composite (1) included in a solid electrolyte membrane (300) according to one embodiment, FIG. 3 is a s