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KR-102961317-B1 - ELECTROLYTE MATERIAL AND METHODS OF FORMING

KR102961317B1KR 102961317 B1KR102961317 B1KR 102961317B1KR-102961317-B1

Abstract

The solid electrolyte material may include a halide material represented by Li 3-xf M f RE 1-y Me k y (Cl 1-upq Br u F p I q ) 6-x+y*(k-3) , and the halide material includes at least two halide anions. The halide material may include a reduced content of one or more impurity phases, including a binary halide phase, an oxyhalide phase, or a ternary halide phase.

Inventors

  • 아사트, 고라브
  • 오스펜스키, 블라디미르

Assignees

  • 세인트-고바인 세라믹스 앤드 플라스틱스, 인크.

Dates

Publication Date
20260508
Application Date
20220517
Priority Date
20210517

Claims (15)

  1. As a solid electrolyte material, It includes a halogenated substance represented as Li af M a' RE b Me' k b' (Cl c Br c' ) 6-f+(k-3)*b' , In the above formula, M is at least one alkali metal element other than Li; RE is at least one rare earth element; Me' is different from M and RE and includes divalent elements, tetravalent elements, trivalent elements, or combinations thereof; (a+a')=3; -1≤f≤1; (c+c')=1; (b+b')=1; c>c'>0; and 0.63≤c/(c+c')≤0.98 and, A solid electrolyte material comprising a water-insoluble impurity phase with a total content of less than 0.11 weight% and a binary halide phase with a total content of 9 weight% or less based on the total weight of the halide material, wherein the binary halide phase comprises lithium halide, rare earth halide, or a combination thereof.
  2. A solid electrolyte material according to claim 1, wherein the halogenated material has a crystallographic phase transition when c/(c+c') is within the stoichiometric range of (c/(c+c')) t * 0.84 to (c/(c+c')) t * 1.16, and in the above formula, (c/(c+c')) t corresponds to a crystallographic phase transition boundary on a crystallographic phase diagram at a temperature of 20°C to 25°C.
  3. A solid electrolyte material according to claim 1, wherein the halogenated material has a crystallographic phase transition when b/(b+b') is within the stoichiometric range of (b/(b+b')) t * 0.84 to (b/(b+b')) t * 1.16, and in the above formula, (b/(b+b')) t corresponds to a crystallographic phase transition boundary on a crystallographic phase diagram at a temperature of 20°C to 25°C.
  4. A solid electrolyte material according to claim 1, wherein the halogenated material has a crystallographic phase transition when a/(a+a') is within the stoichiometric range of (a/(a+a')) t * 0.84 to (a/(a+a')) t * 1.16, and in the above formula, (a/(a+a')) t corresponds to a crystallographic phase transition boundary on a crystallographic phase diagram at a temperature of 20°C to 25°C.
  5. A solid electrolyte material according to claim 1, wherein the total content of the binary halide phase is 2 weight% or less.
  6. As a solid electrolyte material, It includes a halogenated substance represented as Li 3-f RE b Me' k b' (Cl c Br c' ) 6-f+(k-3)*b' , In the above formula, RE is at least one rare earth element; Me' is different from RE and includes divalent elements, tetravalent elements, trivalent elements, or combinations thereof; -1≤f≤1; c≥c'; (c+c')=1; (b+b')=1; b>0; and A solid electrolyte material in which b'>0.
  7. A solid electrolyte material according to claim 6, wherein 0.65 ≤ c/(c+c') ≤ 0.95.
  8. In paragraph 6, a solid electrolyte material wherein RE comprises Y, and Me' comprises In, Yb, Fe, Ti, Sn, Sb, Bi, alkaline earth elements, Hf, or Zr.
  9. As a solid electrolyte material, It includes halogenated substances represented as Li a M a' Me b Me' b' X c X' c' , In the above formula, M is at least one alkali metal element other than Li; Me is different from M and contains rare earth elements; Me' is different from M and Me and includes divalent elements, tetravalent elements, trivalent elements, or combinations thereof; X is a halogen; X' is a halogen other than X; (a+a')>0; (b+b')>0; and c≥c'>0 and; A solid electrolyte material such that when Me' is In, 0.69 ≤ c/(c+c') ≤ 0.95; or when Me' is Yb, 0.65 ≤ c/(c+c') ≤ 0.89; or when Me' is Zr, 0.72 ≤ c/(c+c') ≤ 0.98.
  10. As a solid electrolyte material, It includes a halogenated substance represented as Li a M a' REX 6 , and In the above formula, M is at least one alkali metal element other than Li; X is a halogen; a>a'>0; a+a'=3; and 0.942≤a/(a+a')≤0.958 and; RE is a solid electrolyte material that is at least one rare earth element.
  11. As a solid electrolyte material, It includes halogenated substances represented as Li a M a' RE b Me' b' Cl c X' c' , In the above formula, M is at least one alkali metal element other than Li; RE is at least one rare earth element; Me' is different from M and Me and includes divalent, tetravalent, trivalent elements, or combinations thereof; where Me' has an ionic radius smaller than RE, X' is a halogen other than Cl; a>0; a'≥0; b≥b'>0; and c≥c'>0; The above-mentioned halide material has a crystallographic phase transition when (b/(b+b')) t * 0.84 <b/(b+b')<(b/(b+b')) t * 1.16, wherein (b/(b+b')) t in the above formula corresponds to a crystallographic phase transition boundary on the crystallographic phase diagram at a temperature of 20°C to 25°C, where the crystallographic phase transition includes a transition from Pnma or P-3m1 to C2/m or C2/c, or a transition of the crystallographic structure from orthorhombic to monoclinic; A solid electrolyte material wherein the halide material comprises a binary halide phase having a total content of 2 weight% or less relative to the total weight of the halide material, and the binary halide phase comprises lithium halide, a rare earth halide, or a combination thereof.
  12. As a solid electrolyte material, It includes a halogenated substance represented as Li₃Me₃⁺Cl₆ (1-p) ₆F₆p₆ , and In the above formula, 0<p<0.58 and; A solid electrolyte material comprising one or more water-insoluble impurity phases with a total content of less than 0.11 weight% and a binary halide phase with a total content of 9 weight% or less based on the total weight of the halide material, wherein the binary halide phase comprises lithium halide, rare earth halide, or a combination thereof.
  13. A solid electrolyte material according to claim 12, wherein the total content of the binary halide phase is 2 weight% or less.
  14. A solid electrolyte material according to any one of claims 6 to 10, wherein the halogenated material comprises a binary halide phase with a total content of 2 weight% or less and a water-insoluble impurity phase with a total content of less than 0.11 weight% based on the total weight of the halogenated material.
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Description

Electrolyte Material and Methods of Forming The following relates to a solid electrolyte material and a method for forming the same, and specifically, to a solid electrolyte material comprising a halide material having at least two halide anions and a method for forming the same. With the advent of lithium metal anodes, solid-state lithium batteries are expected to offer higher energy density and faster recharge times, while causing fewer safety issues compared to conventional lithium-ion batteries. Current solid electrolyte materials include oxides, halides, sulfides, fluorides, and solid polymer electrolytes. Oxide-based materials have been considered to be safe and possess excellent chemical and electrochemical stability. The synthesis of these compounds generally utilizes high temperatures exceeding 1,000 to 1,200°C. Oxide-based materials are typically dense, rigid, and brittle, with an ionic conductivity (IC RT ) of up to 1.0 mS/cm at room temperature. Halogen compounds, such as chlorides and bromides, are generally safe and possess excellent chemical and electrochemical stability, deformability at room temperature, and plasticity, thereby enabling relatively high compatibility with active electrode materials. Halides are generally hygroscopic, forming hydrates or undergoing hydrolysis upon exposure to moisture. Halogen solid electrolytes , such as Li₃YCl₆ (LYC) and Li₃YBr₆ ( LYB ), are synthesized using high-energy ball milling-based solid-state synthesis methods. Such synthesis presents difficulties for large-scale production applications because it additionally utilizes expensive binary halide reactants and/or high-temperature annealing. Fluorides are very similar to oxides in physical, chemical, and electrochemical properties, but generally have an IC RT value of less than 1 mS/cm. Sulfides possess relatively high ionic conductivity. For example, IC4RT can be as high as 25 mS/cm, whereas commercially available sulfide or thiophosphate solid electrolytes can achieve 2 to 10 mS/cm. Sulfide materials are mechanically more flexible and deformable. However, sulfide materials have poor electrochemical stability and tend to cause safety issues due to the risk of releasing toxic H2S when they accidentally react with water and heat. Furthermore, high surface area sulfide solid electrolyte powders pose a particularly high H2S risk due to their increased reactivity, even under ambient humidity. Solid polymer electrolytes containing lithium salts generally have relatively low IC RT values and electrochemical stability. The industry continues to demand improved solid electrolyte materials. The present disclosure may be better understood by referring to the accompanying drawings, and many of its features and advantages may become apparent to those skilled in the art. Figures 1a and 1b include examples including readings of XRD patterns of halogenated materials. Figure 2 includes an example including a reading of the XRD pattern of an additional halogenated material. FIG. 3 includes a flowchart illustrating a process for forming a solid electrolyte material according to one embodiment. FIG. 4 includes an example of a portion of a cross-section of an exemplary electrochemical device. Figures 5 and 6 include cyclic voltammetry VA diagrams of a battery sample. FIGS. 7a and FIGS. 7b include examples of exemplary electrochemical devices according to embodiments of the present specification. FIG. 8 includes a diagram of Cl vs. ionic conductivity of a halide material according to one embodiment. Figures 9a and 9b include examples including readings of XRD patterns of additional halogenated materials. FIG. 10 includes an example of a formation process according to one embodiment. FIG. 11a and FIG. 11b include examples of the electrochemical stability of a halogen material. A person skilled in the art understands that elements in the drawings are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to others to help improve understanding of embodiments of the invention. The use of the same reference numeral in different drawings indicates similar or identical items. The following description, in combination with the drawings, is provided to aid in understanding the teachings disclosed herein. The following discussion will focus on specific embodiments and forms of the teachings. This focus is provided to aid in explaining the teachings and should not be construed as a limitation on the scope or availability of the teachings. As used herein, the terms “comprising,” “comprising,” “having,” “having,” “having,” or any other variation thereof are intended to include non-exclusive inclusions. For example, a process, method, article, or apparatus comprising a list of features is not necessarily limited to such features but may include other features not explicitly listed or not unique to such process, method, articl