KR-20260062238-A - SOLID ELECTROLYTE, METHOD OF MANUFACTURING THE SAME AND ALL-SOLID-STATE BATTERY HAVING THE SAME

Abstract

A method for manufacturing a solid electrolyte, a solid electrolyte, and an all-solid-state battery are disclosed. A method for manufacturing a solid electrolyte according to the present invention comprises the steps of: (a) mixing and grinding LiCl and NbOCl₃ as starting materials to obtain an intermediate product; and (b) heat-treating the intermediate product to produce a LiNbOCl₄ solid electrolyte.

Inventors

• 정구진
• 김경수
• 박건호
• 김진규
• 송재혁
• 이규린

Assignees

• 한국전자기술연구원
• 삼성에스디아이 주식회사

Dates

Publication Date

20260507

Application Date

20241028

Claims (11)

1. (a) a step of mixing and grinding LiCl and NbOCl₃ as starting materials to obtain an intermediate product; and (b) A method for manufacturing a chloride-based solid electrolyte comprising the step of heat-treating the above intermediate product to produce a LiNbOCl 4 solid electrolyte.
2. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein the above step (a) is performed by ball milling.
3. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein steps (a) and (b) are performed in a waterless oxygen-free glove box or dry room.
4. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein steps (a) and (b) are performed under an inert gas atmosphere.
5. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein the heat treatment of step (b) above is performed in a temperature range of 100 to 150°C.
6. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein the heat treatment of step (b) above is performed in a temperature range of 120 to 130°C.
7. In paragraph 1, A method for manufacturing a chloride-based solid electrolyte, wherein the heat treatment of step (b) above is performed for 1 to 10 hours.
8. A chloride-based solid electrolyte composed of orthorhombic LiNbOCl₄ , which does not contain NbOCl₃ , LiCl, and Nb₂O₅ in the solid electrolyte or contains 1% or less by weight.
9. In paragraph 8, The above solid electrolyte is a chloride-based solid electrolyte that exhibits an ionic conductivity of 4.3 mS/cm or higher at 25°C.
10. A separator comprising a chloride-based solid electrolyte according to paragraph 8 or 9.
11. anode; cathode; and It includes a solid electrolyte disposed between the anode and the cathode, and The above solid electrolyte comprises a chloride-based solid electrolyte according to claim 8 or 9, in an all-solid-state battery.

Description

Solid electrolyte, method of manufacturing the same, and all-solid-state battery having the same The present invention relates to solid electrolytes, and more specifically, to a technology for manufacturing chloride-based solid electrolytes. In addition, the present invention relates to a chloride-based solid electrolyte containing niobium (Nb). In addition, the present invention relates to an all-solid-state battery comprising a chloride-based solid electrolyte. With the commercialization of electric vehicles, extensive research is being conducted on secondary batteries. Among secondary batteries, lithium-ion batteries, the most representative type, exhibit excellent energy density and power output characteristics. The electrolyte primarily used in lithium-ion batteries is a liquid electrolyte. However, it has been pointed out that these liquid electrolytes decompose due to electrode reactions, causing battery expansion, and pose a risk of ignition due to electrolyte leakage. To address the issues associated with these liquid-type rechargeable batteries, lithium-ion batteries utilizing solid electrolytes with excellent stability—namely, all-solid-state batteries—are attracting attention. While conventional lithium-ion batteries suffer from safety vulnerabilities due to the use of flammable organic liquid electrolytes, all-solid-state batteries are expected to ensure a high level of safety by utilizing non-flammable or flame-retardant solid electrolytes. Solid electrolytes used in all-solid-state batteries can be classified into sulfide-based, oxide-based, and chloride-based types. Among these, chloride-based solid electrolytes use chloride ions ( Cl- ), so they provide improved high-voltage stability compared to sulfide-based or oxide-based solid electrolytes. However, conventional chloride-based solid electrolytes exhibit low lithium-ion conductivity of 10⁻⁵ to10⁻³ S/cm at room temperature compared to sulfide-based solid electrolytes. Therefore, it is necessary to develop chloride-based solid electrolytes with high ionic conductivity. Figure 1 schematically illustrates a method for manufacturing a chloride-based solid electrolyte according to an embodiment of the present invention. Figure 2 shows the powder X-ray diffraction analysis results of solid electrolyte specimens according to the examples and comparative examples. Figure 3 shows the high voltage stability measurement results (cyclic voltammetry) of solid electrolyte specimens according to Example 2 and Comparative Example 1. Figure 4 shows the results of a charge/discharge performance test of an all-solid-state battery using solid electrolyte specimens according to Example 2 and Comparative Example 1. Figure 5 shows the EIS analysis results of an all-solid-state battery with solid electrolyte specimens according to Example 2 and Comparative Example 1. The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but may be implemented in various different forms. These embodiments are 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, and the present invention is defined only by the scope of the claims. Throughout the specification, the same reference numerals refer to the same components. In the drawings, the sizes and relative sizes of layers and regions may be exaggerated for clarity of description. When an element or layer is referred to as another element or "above" or "on top," it includes not only cases where it is directly above another element or layer, but also cases where another layer or element is interposed in between. On the other hand, when an element is referred to as "directly above" or "immediately above," it indicates that no other element or layer is interposed in between. Furthermore, where it is stated that a component is "connected," "combined," or "connected" to another component, it should be understood that said components may be directly connected or connected to each other, but that another component may be "interposed" between each component, or that each component may be "connected," "combined," or "connected" through another component. Spatially relative terms such as "below," "lower," "above," and "upper" may be used to facilitate the description of the relationship between one element or component and another, as illustrated in the drawings. Spatially relative terms should be understood as encompassing different orientations of the element when used or operated, in addition to the orientations illustrated in the drawings. For example, if an element illustrated in the drawings is flipped, an element described as being "below" another element may be placed "above" that other element. Theref