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KR-102963262-B1 - Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the same, and preparation method thereof

KR102963262B1KR 102963262 B1KR102963262 B1KR 102963262B1KR-102963262-B1

Abstract

A solid ion conductor compound comprising Li, P, Hf, and S but not O, wherein some of the P is substituted with Hf, wherein the solid ion conductor compound comprises an azirodite crystal structure phase, a solid electrolyte comprising the same, an electrochemical cell comprising the same, and a method for manufacturing the same are presented.

Inventors

  • 김현석
  • 김소연
  • 키타지마 신타로

Assignees

  • 삼성에스디아이 주식회사

Dates

Publication Date
20260508
Application Date
20200327

Claims (20)

  1. A solid ion conductor compound represented by the following chemical formula 1, wherein the solid ion conductor compound comprises an azirodite crystal structure phase: <Chemical Formula 1> Li a M1 b M2 c P d Hf e S 6-fg N g The above X is one or more elements selected from Group 17 of the periodic table, and The above M1 is one or more metallic elements other than Li selected from Groups 1, 2, and 11 of the periodic table, and The above M2 is one or more elements other than Hf, N, and P selected from Groups 4, 5, 6, 14, and 15 of the periodic table, and 4≤a≤8, b=0, 0≤c<1, 0<d<1, 0<e<1, 0<f<5, 0≤g<1.
  2. In paragraph 1, The above solid ion conductor compound is a solid ion conductor compound having diffraction peaks at diffraction angles 2θ = 15.42°±0.50°, 17.87°±0.50°, 25.48°±0.50°, 30.01°±0.50°, and 31.38°±0.50° in an XRD spectrum using CuKα lines.
  3. delete
  4. delete
  5. delete
  6. In paragraph 1, The above X is a solid ion-conducting compound in which X is F, Cl, Br, I, or a combination thereof.
  7. In paragraph 1, The above f is a solid ion-conducting compound in which 1≤f<3.
  8. In paragraph 1, A solid ion-conducting compound in which 0 < e/(d+e) < 0.5.
  9. delete
  10. In paragraph 1, The above M2 is a solid ion-conducting compound comprising one or more elements selected from Si, Ge, As, Sb, Bi, Sn, Pb, V, Nb, Ta, Cr, Mo, W, Ti, and Zr.
  11. In paragraph 1, A solid ion-conducting compound with c=0.
  12. In paragraph 1, The above solid ion conductor compound is a solid ion conductor compound represented by the following chemical formula 2: <Chemical Formula 2> Li 7+x-(v+y+z) P 1-x Hf x S 6-(v+y+z) N v The above X1 and X2 are one or more elements selected from F, Cl, Br, and I, and 0<x≤0.5, 0<y<2, 0<z<2, 0≤v<1.
  13. In Paragraph 12, The above X1 is Cl, and The above X2 is Cl or Br, and A solid ion-conducting compound for 0 < y + z ≤ 2.
  14. In paragraph 1, The above-mentioned solid ion conductor has an ion conductivity retention rate of 40% or more after 14 days under dry conditions in an air atmosphere having a dew point of less than -40℃, and A solid ion-conducting compound, wherein the above ion conductivity retention rate is represented by the following mathematical formula 1. <Mathematical Formula 1> Ion conductivity retention rate = [Ion conductivity of solid ion-conducting compound after 14 days / Ion conductivity of solid ion-conducting compound at initial] × 100
  15. In paragraph 1, Solid ion-conducting compounds represented by any one of the following chemical formulas: Li 7+xy P 1-x Hf x S 6-y Cl y , Li 7+xy P 1-x Hf x S 6-y Br y, Li 7+xy P 1-x Hf x S 6-y I y; Li 7+x-(y+z) P 1-x Hf x S 6 -yz Cl y Br z , Li 7 + x-(y+z ) P 1 - x Hf 6-(v+y) N v Cl y , Li 7+x-(v+y) P 1-x Hf x S 6- (v+y) N v Br y , Li 7+x- ( v+y ) P 1- x Hf , Li 7+x-(v+y+z) P 1-x Hf x S 6-(v+y+z) N v Cl y I z ,Li 7+x- (v+y+z) P 1 - x Hf In the above equations, 0<x≤0.5, 0<y<2, 0<z<2, and 0<v<1.
  16. In paragraph 1, Li 5.85 P 0.9 Hf 0.1 S 4.75 Cl 1.25 , Li 5.95 P 0.8 Hf 0.2 S 4.5 Cl 1.25 , Li 5.6 P 0.9 Hf 0.1 S 4.5 Cl 1.5, Li 5.85 P 0.9 Hf 0.1 S 4.75 Br 1.25 , Li 5.95 P 0.8 Hf 0.2 S 4.5 Br 1.25 , Li 5.6 P 0.9 Hf 0.1 S 4.5 Br 1.5, Li 5.85 P 0.9 Hf 0.1 S 4.75 I 1.25 , Li 5.95 P 0.8 Hf 0.2 S 4.5 I 1.25 , Li 5.6 P Solid ion conductor compounds selected from 0.9 Hf 0.1 S 4.5 I 1.5, Li 5.6 P 0.9 Hf 0.1 S 4.5 Cl 0.5 Br, Li 5.6 P 0.9 Hf 0.1 S 4.5 Cl 0.5 I , Li 5.6 P 0.9 Hf 0.1 S 4.5 Br 0.5 I , Li 5.95 P 0.9 Hf 0.1 N 0.1 S 4.65 Cl 1.25 , Li 6.05 P 0.8 Hf 0.2 N 0.1 S 4.4 Cl 1.25 , and Li 5.7 P 0.9 Hf 0.1 N 0.1 S 4.4 Cl 0.5 Br.
  17. A solid electrolyte comprising a solid ion-conducting compound according to any one of claims 1, 2, 6 to 8 and 10 to 16.
  18. Anode layer including an anode active material layer; A cathode layer comprising a cathode active material layer disposed on a cathode current collector; and It includes an electrolyte layer disposed between the anode layer and the cathode layer, and An electrochemical cell in which the positive active material layer and the electrolyte layer comprise a solid ion conductor compound according to any one of claims 1, 2, 6 to 8 and 10 to 16.
  19. In Paragraph 18, An electrochemical cell in which the above electrochemical cell is an all-solid-state secondary battery.
  20. In claim 18, the negative electrode active material layer comprises a negative electrode active material and a binder, An electrochemical cell in which the above-mentioned cathode active material is a mixture of amorphous carbon and one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn) and zinc (Zn).

Description

Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the same, and preparation method thereof The invention relates to a solid ion-conducting compound, a solid electrolyte containing the same, a lithium battery containing the same, and a method for manufacturing the same. All-solid-state lithium batteries contain a solid electrolyte. Since all-solid-state lithium batteries do not contain flammable organic solvents, they offer excellent stability. Conventional solid electrolyte materials are not sufficiently stable with respect to lithium metal and degrade in the atmosphere due to their high reactivity with moisture. Furthermore, the lithium ion conductivity of conventional solid electrolytes is lower than that of liquid substitutes. Figure 1 is a powder XRD spectrum of the solid ion conductor compounds prepared in Examples 1 to 4. FIG. 2 is a graph showing the ionic conductivity measurement results for solid ion conductor compounds prepared in Examples 1 to 4 and Comparative Examples 1 and 2. Figure 3 is a graph of the capacity retention rate according to charging and discharging of the all-solid-state secondary batteries prepared in Example 5 and Comparative Example 3. Figure 4 is a graph showing the lifespan characteristics of all-solid-state secondary batteries prepared in Examples 5 and 6, and Comparative Examples 3 and 4. FIG. 5 is a schematic diagram of one embodiment of an all-solid-state secondary battery. FIG. 6 is a schematic diagram of another embodiment of an all-solid-state secondary battery. FIG. 7 is a schematic diagram of another embodiment of an all-solid-state secondary battery. <Explanation of symbols for major parts of the drawing> 1, 1a: All-solid-state secondary battery 10: Cathode 11: Positive current collector 12: Positive active material layer 20: Cathode 21: Cathode current collector 22: Cathode active material layer 23: Metal layer 30: Solid electrolyte layer 40: All-solid-state secondary battery 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 relative terms such as "bottom," "lower," "subordinate," "top," "upper," and "upper" may be used herein to facilitate the description of the relationship of one component or feature to another component or feature. Spatially relative terms are to be understood as intended to include different orientations of the device during use or operation in addition to the orientations depicted in the drawings. For example, if the device in the drawings is inverted, a component described as "bottom" or "lower" of another component or feature will be oriented to the "top" of that other component or feature. Thus, the exemplary term "bottom" may encompass both the upper and lower directions. The device may be positioned in different directions (it may be rotated 90 degrees or rotated in other direc