Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the same, and method of preparing the same

Patent metadata

Field	Value
Publication number	US-12456751-B2
Application number	US-202117509537-A
Country	US
Kind code	B2
Filing date	Oct 25, 2021
Priority date	Nov 12, 2020
Publication date	Oct 28, 2025
Grant date	Oct 28, 2025

Abstract

A solid ion conductor compound represented by Formula 1:LixM1aM2bClyBrz  Formula 1wherein M1 is an alkali metal, an alkaline earth metal, a transition metal, or a combination thereof, M2 is a lanthanide element, or a combination thereof, 0<x<3.5, 0≤a<1.5, 0<b<1.5, 0<y<6, 0<z<6, and 0.166<y/z≤5.

First claim

What is claimed is:

1. A solid ion conductor compound represented by Formula 1:
Li x M1 a M2 b Cl y Br z   Formula 1

wherein M1 comprises Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, or a combination thereof,
M2 comprises La, Ce, Pr, Nd, Pm, Eu, Dy, Ho, Er, Tm, Yb, Lu, or a combination thereof,
0<x<3.5, 0≤a<1.5, 0<b<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
wherein the solid ion conductor compound has an ionic conductivity of 10 −4 Siemens per centimeter or greater at −20° C. to 40° C., and
wherein the solid ion conductor compound does not have a diffraction peak at 40°2θ to 44°2θ, when analyzed by X-ray diffraction using CuKα radiation,
wherein the solid ion conductor compound comprises a phase having a crystal structure that belongs to a C2/m space group, and a phase having a crystal structure that belongs to a P3 m1 space group.

2. The solid ion conductor compound of claim 1 , wherein M2 comprises La, Ho, Tm, Yb, Lu, or a combination thereof.

3. The solid ion conductor compound of claim 1 , wherein in Formula 1, a portion of the Li crystallographic sites are occupied by M1.

4. The solid ion conductor compound of claim 1 , wherein M1 comprises Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, or a combination thereof.

5. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound comprises:
Li x HoCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x CeCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x PrCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x NdCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x PmCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x EuCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x DyCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x ErCl y Br z where 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x TmCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x YbCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34,
Li x LuCl y Br z wherein 0<x<3.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34;
Li x M1 a HoCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a CeCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a PrCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a NdCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a PmCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a EuCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a DyCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a ErCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, —Li x M1 a TmCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a YbCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, Li x M1 a LuCl y Br z wherein 0<x<3.5, 0≤a<1.5, 0<y<6, 0<z<6, and 0.16<z/(y+z)<0.34, wherein M1 is independently Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, or a combination thereof; or
a combination thereof.

6. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has an ionic conductivity of 1.8×10 −4 Siemens per centimeter or greater at −20° C. to 40° C.

7. A solid electrolyte comprising a layer comprising the solid ion conductor compound according to claim 1 .

8. An electrochemical cell comprising:
a positive electrode layer including a positive electrode active material layer;
a negative electrode layer including a negative electrode active material layer; and
an electrolyte layer located between the positive electrode layer and the negative electrode layer,
wherein the positive electrode active material layer, the electrolyte layer, or a combination thereof comprise the solid ion conductor of claim 1 .

9. The electrochemical cell of claim 8 , wherein the negative electrode layer comprises lithium metal, a lithium metal alloy, or a combination thereof.

10. The electrochemical cell of claim 8 , wherein the electrochemical cell is an all-solid secondary battery.

11. A protected positive electrode comprising:
a current collector;
a positive electrode layer including a positive electrode active material; and
a protection layer comprising the solid ion conductor compound of claim 1 on the positive electrode layer.

12. A protected negative electrode comprising:
a current collector;
a negative electrode layer including a negative electrode active material; and
a protection layer comprising the solid ion conductor compound of claim 1 on the negative electrode layer.

13. The solid ion conductor compound of claim 1 , wherein M2 is Ho, Tm, Yb, Lu, or a combination thereof.

14. The solid ion conductor compound of claim 1 , wherein the indice a is zero or 0<a≤0.2.

15. A method of preparing the solid ion conductor of claim 1 , the method comprising:
mixing a lithium precursor and a lanthanide-element-containing precursor to prepare a mixture; and
treating the mixture to prepare the solid ion conductor.

16. The method of claim 15 , wherein the treating comprises ball-mill mixing the mixture in a dry and inert atmosphere.

17. The method of claim 15 , further comprising, after the treating, heat-treating for 4 to 6 hours at about 200° C. to about 300° C.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Yoon Gabin
• Kim Jusik

Classifications

• H01M2300/008

  Halides · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/405

  Alloys based on lithium · CPC title

• H01M4/366

  as layered products · CPC title