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US-12626952-B2 - Solid ion conductor compound, electrochemical cell comprising the same, and preparation method thereof

US12626952B2US 12626952 B2US12626952 B2US 12626952B2US-12626952-B2

Abstract

A solid ion conductor compound represented by Formula 1, an electrochemical cell including the same, and a method of preparing the solid ion conductor compound. The solid ion conductor is a compound of Formula 1 Li a M b Zr c X d T e Formula 1 wherein in Formula 1, 1<a<3.5, 0<b<1.5, 0<c<1.5, 0<d<7, 0≤e<1, 0<b/d<0.03, and 0.05<c/d<0.18, M is at least one monovalent metal element other than lithium, and T is a metal element different from M, a transition metal element, a post-transition metal element, a metalloid element, or a combination thereof, wherein an ionic radius of M satisfies 90 pm<M r ≤180 pm, wherein M r is an ionic radius of M, and X is at least one halogen.

Inventors

  • Wonsung Choi
  • Jusik Kim
  • Gabin Yoon

Assignees

  • SAMSUNG ELECTRONICS CO., LTD.

Dates

Publication Date
20260512
Application Date
20221129
Priority Date
20211201

Claims (20)

  1. 1 . A solid ion conductor compound represented by Formula 1: Li a M b Zr c X d T e Formula 1 wherein in Formula 1, 1<a<3.5, 0<b<1.5, 0<c<1.5, 0<d<7, 0≤e<1, 0<b/d<0.03, and 0.05<c/d<0.18, M is at least one monovalent metal element other than lithium, and T is a metal element different from M, a transition metal element, a post-transition metal element, a metalloid element, or a combination thereof, wherein an ionic radius of M satisfies 90 pm<M r ≤180 μm, wherein M r is an ionic radius of M, and X is at least one halogen.
  2. 2 . The solid ion conductor compound of claim 1 , wherein M comprises Na, K, Rb, Mo(I), Cu(I), Hg, Ag, Au, Tl, or a combination thereof.
  3. 3 . The solid ion conductor compound of claim 1 , wherein T is B, Be, Mg, Ca, Sr, Se, Y, Ti, Hf, V, Nb, Ta, Cr, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cd, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Po, or a combination thereof.
  4. 4 . The solid ion conductor compound of claim 1 , wherein X comprises Cl, Br, or a combination thereof.
  5. 5 . The solid ion conductor compound of claim 1 , wherein M r satisfies 90 pm<M r ≤160 pm.
  6. 6 . The solid ion conductor compound of claim 1 , wherein a satisfies 1.5≤a≤2.5, b satisfies 0<b<0.5, c satisfies 0.1≤c<1.5, and d satisfies 5<d<7.
  7. 7 . The solid ion conductor compound of claim 1 , wherein e satisfies 0<e<1.
  8. 8 . The solid ion conductor compound of claim 1 , wherein 0.01≤b/d≤0.02.
  9. 9 . The solid ion conductor compound of claim 1 , wherein 0.06≤c/d≤0.17.
  10. 10 . The solid ion conductor compound of claim 1 , wherein 1<a/c<5.
  11. 11 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has at least one diffraction peak at diffraction angles of about 15°2θ to about 17°2θ, about 30° 2θ to about 32°2θ, and about 40° 2θ to about 42°2θ, when analyzed by X-ray diffraction using CuKα radiation.
  12. 12 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has a diffraction peak at diffraction angles of 16.0°2θ+2.0°2θ, 30.4°2θ+2.0°2θ, 31.8°2θ+2.0°2θ, 34.1°2θ+2.0°2θ, 41.3°2θ+2.0° 2θ, and 49.4°2θ +2.0° 2 θ when analyzed by X-ray diffraction using CuKα radiation.
  13. 13 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound comprises a crystalline phase, or a combination of crystalline phase and amorphous phase.
  14. 14 . The solid ion conductor compound of claim 13 , wherein the crystalline phase comprises a layered rock-salt crystal structure.
  15. 15 . The solid ion conductor compound of claim 13 , wherein the crystalline phase comprises a crystal of a C2/m space group, a crystal of a P3m1 space group, or a combination thereof.
  16. 16 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has an a-axis lattice constant and a c-axis lattice constant that are each greater than an a-axis lattice constant and a c-axis lattice constants when the at least one monovalent metal element M is not present.
  17. 17 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has an ionic conductivity of 2.4×10 −4 S/cm or more at 25° C.
  18. 18 . The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound is Li 1.96 Na 0.03 ZrCl 6 , Li 1.96 Na 0.04 ZrCl 6 , Li 1.9 Na 0.1 ZrCl 6 , Li 2 Na 0.04 Zr 0.99 Cl 6 , Li 2 Na 0.1 Zr 0.98 Cl 6 , Li 1.96 Cu 0.04 ZrCl 6 , Li 2 Cu 0.04 Zr 0.99 Cl 6 , Li 1.96 Ag 0.04 ZrCl 6 , Li 1.96 K 0.04 ZrCl 6 , Li 1.96 Na 0.04 Y 0.5 Zr 0.5 Cl 6 , Li 1.9 K 0.1 ZrCl 6 , Li 1.85 K 0.15 ZrCl 6 , Li 2.36 Na 0.04 Zr 0.9 Cl 6 , or Li 2.45 Na 0.05 Zr 0.5 Cl 6 Y 0.5 .
  19. 19 . A method of preparing a solid ion conductor compound, the method comprising: providing a mixture of a zirconium precursor compound, a lithium precursor compound, and a metal element M precursor compound, wherein the metal element M is at least one monovalent metal element other than lithium, and an ionic radius of the metal element M satisfies 90 pm<M r ≤180 μm, wherein M r is an ionic radius of M; and treating the mixture to form the solid ion conductor compound.
  20. 20 . The method of claim 19 , wherein the treating comprises ball-milling the mixture in a dry and inert atmosphere.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is based on and claims priority to Korean Patent Application No. 10-2021-0170364, filed on Dec. 1, 2021, and Korean Patent Application No. 10-2022-0127173, filed on Oct. 5, 2022, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which are incorporated by reference herein in their entirety. BACKGROUND 1. Field Disclosed is a solid ion conductor compound, an electrochemical cell including the same, and a method of preparing the same. 2. Description of the Related Art Electrochemical cells, for example, all-solid-state batteries include a solid electrolyte as an electrolyte. All-solid-state batteries do not contain flammable organic solvents, and thus exhibit excellent stability. Solid electrolyte materials in the art are limited in that they are not sufficiently stable with respect to lithium metal and have low lithium ion conductivity. To address the aforementioned and other issues, sulfide-based solid electrolytes, halogen-based solid electrolytes, and oxide-based solid electrolytes have been studied. In particular, sulfide-based solid electrolytes and oxide-based solid electrolytes have the advantage of having high ionic conductivity, but sulfide-based solid electrolytes generate toxic gas by reacting with water, and oxide-based solid electrolytes have low formability. In contrast, halogen-based solid electrolytes have attracted attention in that they do not react with water to generate toxic gas and yet exhibit excellent formability. However, the halogen-based solid electrolytes developed thus far are limited in that they do not have satisfactory ionic conductivity, or have insufficient stability. In this context, there is a need for a halogen-based solid electrolyte having high ionic conductivity and improved stability. SUMMARY Provided are a novel solid ion conductor compound having excellent lithium ion conductivity, an electrochemical cell including the same, and a method of preparing the same. Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure. According to one aspect, provided is a solid ion conductor compound represented by Formula 1. LiaMbZrcXdTe  Formula 1 In Formula 1, 1<a<3.5, 0<b<1.5, 0<c<1.5, 0<d<7, 0≤e<1, 0<b/d<0.03, and 0.05<c/d<0.18, M is at least one monovalent metal element other than lithium, and T is a metal element different from M, a transition metal element, a post-transition metal element, a metalloid element, or a combination thereof, wherein an ionic radius of M is 90 pm<Mr≤180 pm, wherein Mr is an ionic radius of M, and X is at least one halogen element. According to another aspect, provided is a method of preparing a solid ion conductor compound, the method including: providing a mixture of a zirconium precursor compound, a lithium precursor compound, and a metal M precursor compound, wherein the metal element M is at least one monovalent metal element other than lithium, and the metal element M has an ionic radius of 90 pm<Mr<180 pm, wherein Mr is an ionic radius of M; and treating the mixture to form the solid ion conductor compound. According to another aspect, provided is an electrochemical cell including: a cathode layer including a cathode active material layer; an anode layer including an anode active material layer; and a solid electrolyte layer disposed between the cathode layer and the anode layer, wherein at least one of the cathode layer and the solid electrolyte layer includes the solid ion conductor compound. Here, the electrochemical cell may be, for example, an all-solid-state secondary battery, a secondary battery containing a liquid electrolyte, or a lithium-air battery. Also disclosed is a cathode active material layer including the solid ion conductor compound. Also disclosed is a cathode-electrolyte subassembly including the cathode active material layer and an electrolyte layer on the cathode active material layer, the electrolyte including the solid ion conductor compound. BRIEF DESCRIPTION OF THE DRAWINGS The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which: FIG. 1 is a graph of intensity (arbitrary units, a.u.) versus diffraction angle (°2θ) showing an XRD spectrum for the solid ion conductor compounds prepared in Example 1 and Comparative Examples 1 and 2. FIG. 2 is a graph of intensity (arbitrary units, a.u.) versus diffraction angle (°2θ) showing a shift in Example 1 and Comparative Example 2 with respect to the position of the peaks at 32.3°2θ of Comparative Example 1 of the XRD spectrum of FIG. 1. FIG. 3 is a graph of lattice spacing (Angstroms, A) versus lattice constant showing a crystal lattice constant of t