KR-102963263-B1 - All Solid secondary battery

KR102963263B1KR 102963263 B1KR102963263 B1KR 102963263B1KR-102963263-B1

Abstract

An all-solid-state secondary battery is presented, comprising: a positive electrode layer; a negative electrode layer; and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein the positive electrode layer comprises a positive current collector and a positive active material layer disposed on one or both sides of the positive current collector, wherein at least one of the positive active material layer and the solid electrolyte layer comprises a first two-dimensional sulfide-based solid electrolyte, and the negative electrode layer comprises a negative current collector and a first negative active material layer disposed on one side of the negative current collector, wherein the initial charge capacity (B) of the first negative active material layer is less than 50% of the initial charge capacity (A) of the positive active material layer.

Inventors

손인혁
조성님
심규은
임형섭
박태현
이지은

Assignees

삼성에스디아이 주식회사

Dates

Publication Date: 20260511
Application Date: 20230503
Priority Date: 20230326

Claims (20)

It comprises an anode layer; a cathode layer; and a solid electrolyte layer disposed between the anode layer and the cathode layer, The above positive layer comprises a positive current collector and a positive active material layer disposed on one or both sides of the positive current collector, and One or more of the above positive active material layer and the above solid electrolyte layer include a first two-dimensional sulfide-based solid electrolyte, and The above-mentioned cathode layer comprises a cathode current collector and a first cathode active material layer disposed on one surface of the cathode current collector, and The initial charge capacity (B) of the first negative electrode active material layer is less than 50% of the initial charge capacity (A) of the positive electrode active material layer, and The above-mentioned first two-dimensional sulfide-based solid electrolyte comprises a core and a shell disposed on the core, and All-solid-state secondary battery, wherein one or more of the core and shell comprises a sulfide-based solid electrolyte.
In claim 1, the first two-dimensional sulfide-based solid electrolyte is defined by its length and thickness, and The aspect ratio of the above length and thickness is 3 or greater, and The first two-dimensional sulfide-based solid electrolyte has a length of 1 to 50 μm and a thickness of 10 nm to 30 μm, and An all-solid-state secondary battery in which the first two-dimensional sulfide-based solid electrolyte comprises a plate structure, a flake structure, or a combination thereof.
In claim 1, the surface of the first two-dimensional sulfide-based solid electrolyte has an irregular, circular, or polygonal shape, and All-solid-state secondary battery, wherein the above polygonal shape includes a triangle, square, pentagon, hexagon, heptagon, octagon, nonagon, or decagon.
In Article 1, The above core comprises a carbon-based material, a polymer, a metal-containing inorganic material, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, or a combination thereof, and The above shell comprises a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a coating material, or a combination thereof, and The above core includes a two-dimensional nanostructure, and An all-solid-state secondary battery in which the above-mentioned two-dimensional nanostructure comprises graphene, graphene oxide, reduced graphene oxide, carbon nanobelts, carbon nanosheets, carbon nanoplates, carbon nanoflakes, SiO2 , TiO2 , Al2O3 , AlN, SiC, BaTiO3 , or a combination thereof.
In claim 4, the ratio of the first thickness of the core to the second thickness of the shell is 1:0.01 to 1:1000, and All-solid-state secondary battery, wherein the ratio of the first length of the core to the second length of the shell is 1:1 to 1:100.
In claim 1, the positive active material layer comprises a first region adjacent to the positive current collector and a second region adjacent to the solid electrolyte layer, A first two-dimensional sulfide-based solid electrolyte is disposed in the first region and the first two-dimensional sulfide-based solid electrolyte is absent (free) in the second region, A first two-dimensional sulfide-based solid electrolyte is disposed in the second region above, and the first two-dimensional sulfide-based solid electrolyte is absent (free) in the first region, or An all-solid-state secondary battery in which the first two-dimensional sulfide-based solid electrolyte is disposed in the first region and the second region.
In claim 1, the content of the first two-dimensional sulfide-based solid electrolyte is 1 to 50 wt% of the total weight of the anode active material layer, and The above positive active material layer further comprises an irregularly shaped sulfide-based solid electrolyte that is distinct from the first two-dimensional sulfide-based solid electrolyte, and An all-solid-state secondary battery having a weight ratio of the first two-dimensional sulfide-based solid electrolyte and the amorphous sulfide-based solid electrolyte of 1:99 to 99:1.
In claim 1, the positive electrode active material layer comprises a positive electrode active material, The above-mentioned cathode active material includes an oxide-based cathode active material, a sulfide-based cathode active material, or a combination thereof, and The oxide-based cathode active material comprises a lithium transition metal oxide, a metal oxide, or a combination thereof, wherein the lithium transition metal oxide comprises lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt mangense oxide, lithium manganate, lithium iron phosphate, or a combination thereof, and the metal oxide comprises iron oxide, vanadium oxide, or a combination thereof. An all-solid-state secondary battery in which the above-mentioned sulfide-based cathode active material comprises nickel sulfide, copper sulfide, Li₂S , a Li₂S -containing complex, or a combination thereof.
In claim 8, the all-solid-state secondary battery wherein the Li2S-containing composite comprises a composite of Li2S and carbon, a composite of Li2S, carbon and a solid electrolyte, a composite of Li2S and a solid electrolyte, a composite of Li2S and a lithium salt, a composite of Li2S, a lithium salt and carbon, a composite of Li2S and a metal carbide, a composite of Li2S, carbon and a metal carbide, a composite of Li2S and a metal nitride, a composite of Li2S, carbon and a metal nitride, or a combination thereof.
In claim 8, the Li₂S -containing complex further comprises a second two-dimensional sulfide-based solid electrolyte, and A solid-state secondary battery in which the size of the second two-dimensional sulfide-based solid electrolyte is smaller than the size of the first two-dimensional sulfide-based solid electrolyte.
In claim 1, the positive active material layer further comprises one or more selected from a conductive material and a binder, and A solid-state secondary battery in which the above-mentioned conductive material includes a carbon-based conductive material.
In claim 1, it further comprises an inactive member disposed on one side of the anode layer, and The above inert member is arranged to surround the anode layer along the side of the anode layer, and An all-solid-state secondary battery comprising a positioning member configured to determine the position of the inert member on the solid electrolyte layer.
A solid-state secondary battery according to claim 1, comprising a first two-dimensional sulfide-based solid electrolyte in which the solid electrolyte layer is arranged along one direction.
In claim 13, the first two-dimensional sulfide-based solid electrolyte is aligned in a direction orthogonal to the thickness direction of the solid electrolyte layer, and The above-mentioned first two-dimensional sulfide-based solid electrolyte is stacked in the thickness direction of the solid electrolyte layer, and An all-solid-state secondary battery in which the content of the first two-dimensional sulfide-based solid electrolyte is 50 wt% or more of the total weight of the solid electrolyte layer.
In claim 1, the first negative electrode active material layer comprises a negative electrode active material and a binder, and An all-solid-state secondary battery in which the above-mentioned negative electrode active material has a particle form and the average particle size of the above-mentioned negative electrode active material is 4 μm or less.
In claim 15, the cathode active material comprises one or more selected from carbon-based cathode active materials and metal-based cathode active materials, and The above carbon-based negative electrode active material comprises amorphous carbon, crystalline carbon, porous carbon, or a combination thereof, and An all-solid-state secondary battery in which the above-mentioned metal-based negative electrode active material comprises gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), or a combination thereof.
In claim 15, the cathode active material comprises a mixture of first particles made of amorphous carbon and second particles made of metal, and A solid-state secondary battery in which the content of the second particle is 8 to 60 weight% based on the total weight of the mixture.
In claim 15, the negative electrode active material comprises a carbon-based support; and a metal-based negative electrode active material supported on the carbon-based support, The above-mentioned metal-based negative electrode active material comprises a metal, a metal oxide, a composite of a metal and a metal oxide, or a combination thereof, and The above metal-based negative electrode active material has a particle form, and the particle size of the above metal-based negative electrode active material is 1 nm to 200 nm, and All-solid-state secondary battery, wherein the carbon-based support has a particle form and the particle size of the carbon-based support is 10 nm to 2 µm.
In claim 1, it further comprises a second negative electrode active material layer disposed between the solid electrolyte layer and the negative electrode current collector, The second negative electrode active material layer is disposed in one or more of the range between the first negative electrode active material layer and the negative current collector and between the first negative electrode active material layer and the solid electrolyte layer, and The above-mentioned second negative electrode active material layer is a metal layer comprising lithium metal or a lithium alloy, an all-solid-state secondary battery.
In claim 1, one or more of the positive current collector and the negative current collector comprise a base film and a metal layer disposed on one or both sides of the base film, and The above base film comprises a polymer, wherein the polymer comprises polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof, An all-solid-state secondary battery in which the metal layer comprises indium (In), copper (Cu), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

Description

All Solid secondary battery This is about all-solid-state secondary batteries. Recently, there has been active development of batteries that offer increased energy density and safety. Lithium batteries are used in information devices, communication devices, and automobiles. Since automobiles are related to human life, safety is critical. Lithium batteries containing liquid electrolytes contain flammable organic solvents. Lithium batteries containing liquid electrolytes have a high potential for overheating and fire in the event of a short circuit. Solid electrolytes have reduced overheating and fire risk in the event of a short circuit compared to liquid electrolytes. Lithium batteries containing solid electrolytes can provide improved safety compared to lithium batteries containing liquid electrolytes. FIG. 1 is a schematic diagram of a two-dimensional sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 2 is a schematic diagram of a two-dimensional sulfide-based solid electrolyte with a core/shell structure according to an exemplary embodiment. FIG. 3 is a cross-sectional view of a two-dimensional sulfide-based solid electrolyte with a core/shell structure according to an exemplary embodiment. FIG. 4 is a schematic diagram of a two-dimensional sulfide-based solid electrolyte with a core/intermediate layer/shell structure according to an exemplary embodiment. FIGS. 5a to 5c are cross-sectional views of an anode active material layer comprising a two-dimensional sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 6 is a cross-sectional view of a solid electrolyte layer comprising a two-dimensional sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 7 is a cross-sectional view of a solid electrolyte layer comprising an irregularly shaped sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 8 is a schematic diagram of a solid electrolyte layer comprising a two-dimensional sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 9 is a schematic diagram of a solid electrolyte layer comprising an irregularly shaped sulfide-based solid electrolyte according to an exemplary embodiment. FIG. 10 is a cross-sectional view of an all-solid-state secondary battery according to an exemplary embodiment. FIG. 11 is a cross-sectional view of a bi-cell all-solid-state secondary battery according to an exemplary embodiment. FIG. 12 is a cross-sectional view of an all-solid-state secondary battery according to an exemplary embodiment. FIG. 13 is a cross-sectional view of an all-solid-state secondary battery according to an exemplary embodiment. FIG. 14 is a cross-sectional view of a bi-cell all-solid-state secondary battery according to an exemplary embodiment. Various embodiments are illustrated in the accompanying drawings. However, the present creative concept may be embodied in many different forms and should not be interpreted as being limited to the embodiments described herein. Rather, these embodiments are provided to ensure that the present disclosure is thorough and complete and will sufficiently convey the scope of the present creative concept to those skilled in the art. Identical reference numerals denote identical components. When it is stated that one component is "on top" of another component, it can be understood that it may be directly on top of the other component or that another component may be interposed between them. In contrast, when it is stated that a component is "directly on top" of another component, no component is interposed between them. Terms such as "first," "second," "third," etc., may be used in this specification to describe various components, components, regions, layers, and/or zones, but these components, components, regions, layers, and/or zones should not be limited by these terms. These terms are used solely to distinguish one component, component, region, layer, or zone from another. Accordingly, the first component, component, region, layer, or zone described below may be referred to as the second component, component, region, layer, or zone without departing from the teachings of this specification. The terms used herein are intended to describe specific embodiments only and are not intended to limit the creative idea. The singular form used herein is intended to include the plural form including "at least one" unless the content clearly indicates otherwise. "At least one" should not be interpreted as limiting to the singular. As used herein, the term "and/or" includes any combination of one or more of the listed items. The terms "comprising" and/or "comprising" as used in the detailed description specify the presence of the specified features, regions, integers, steps, actions, components, and/or components, and do not exclude the presence or addition of one or more other features, regions, integers, steps, actions, components, components, and/or groups thereof. Spatially r