Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor

Patent metadata

Field	Value
Publication number	US-11735765-B2
Application number	US-202117412400-A
Country	US
Kind code	B2
Filing date	Aug 26, 2021
Priority date	Jan 8, 2021
Publication date	Aug 22, 2023
Grant date	Aug 22, 2023

Abstract

A solid ion conductor, a solid electrolyte and an electrochemical device including the solid ion conductor, and a method of preparing the solid ion conductor are disclosed. The solid ion conductor may include a compound represented by Formula 1:

Li a M b M′ c Zr d X e   Formula 1
wherein, M is one or more metals of Na, K, Cs, Cu, or Ag, and having an oxidation state of +1, M′ is one or more lanthanide metals having an oxidation state of +3 and a crystal ionic radius of about 104 picometers to about 109 picometers, X is one or more halogen elements, 1<a<3.5, 0≤b<1, 0<c<1.5, 0<d<1.5, and 0<e<7.

First claim

What is claimed is:

1. A solid ion conductor comprising one or more compounds having a distorted rock-salt type structure represented by Formula 2 or Formula 3:
Li 2+x M′ x Zr 1-x X y   Formula 2

wherein in Formula 2,
M′ is one or more of lanthanide metals having an oxidation state of +3 and a crystal ionic radius of about 104 picometers to about 109 picometers,
X is one or more halogen elements,
0<x<1, and 0<y<7,
Li p-q M q M′ r Zr 1-r X w   Formula 3

wherein in Formula 3,
M is one or more metals of Na, K, Cs, Cu, or Ag, and having an oxidation state of +1,
M′ is one or more lanthanide metals having an oxidation state of +3 and a crystal ionic radius of about 104 picometers to about 109 picometers,
X is one or more halogen elements,
1<p<3, 0≤q<1, 0<r<1, and 0<w<7.

2. The solid ion conductor of claim 1 , wherein
M′ has an oxidation state of +3 and is one or more of Ho, Dy, Tb, Eu, or Gd,
X in Formula 2 or Formula 3 is one or more of Cl or Br.

3. The solid ion conductor of claim 1 , wherein
the compound comprises one or more of Li 2.7 Ho 0.7 Zr 0.3 Cl 6 , Li 2.5 Ho 0.5 Zr 0.5 Cl 6 , Li 2.3 Ho 0.3 Zr 0.7 Cl 6 , Li 2.25 Ho 0.25 Zr 0.75 Cl 6 , Li 2.2 Ho 0.2 Zr 0.8 Cl 6 , Li 2.15 Ho 0.15 Zr 0.85 Cl 6 , Li 2.25 Ho 0.05 Zr 0.9 Cl 6 , Li 2.1 Ho 0.1 Zr 0.9 Cl 6 , Li 2.05 Ho 0.05 Zr 0.95 Cl 6 , Li 2 Na 0.1 Ho 0.1 Zr 0.9 Cl 6 ;
Li 2.7 Dy 0.7 Zr 0.3 Cl 6 , Li 2.5 Dy 0.5 Zr 0.5 Cl 6 , Li 2.3 Dy 0.3 Zr 0.7 Cl 6 , Li 2.25 Dy 0.25 Zr 0.75 Cl 6 , Li 2.2 Dy 0.2 Zr 0.8 Cl 6 , Li 2.15 Dy 0.15 Zr 0.85 Cl 6 , Li 2.25 Dy 0.05 Zr 0.9 Cl 6 , Li 2.1 Dy 0.1 Zr 0.9 Cl 6 , Li 2.05 Dy 0.05 Zr 0.95 Cl 6 ;
Li 2.7 Tb 0.7 Zr 0.3 Cl 6 , Li 2.5 Tb 0.5 Zr 0.5 Cl 6 , Li 2.3 Tb 0.3 Zr 0.7 Cl 6 , Li 2.25 Tb 0.25 Zr 0.75 Cl 6 , Li 2.2 Tb 0.2 Zr 0.8 Cl 6 , Li 2.15 Tb 0.15 Zr 0.85 Cl 6 , Li 2.25 Tb 0.05 Zr 0.9 Cl 6 , Li 2.1 Tb 0.1 Zr 0.9 Cl 6 , Li 2.05 Tb 0.05 Zr 0.95 Cl 6 ;
Li 2.7 Eu 0.7 Zr 0.3 Cl 6 , Li 2.5 Eu 0.5 Zr 0.5 Cl 6 , Li 2.3 Eu 0.3 Zr 0.7 Cl 6 , Li 2.25 Eu 0.25 Zr 0.75 Cl 6 , Li 2.2 Eu 0.2 Zr 0.8 Cl 6 , Li 2.15 Eu 0.15 Zr 0.85 Cl 6 , Li 2.25 Eu 0.05 Zr 0.9 Cl 6 , Li 2.1 Eu 0.1 Zr 0.9 Cl 6 , Li 2.05 Eu 0.05 Zr 0.95 Cl 6 ; or
Li 2.7 Gd 0.7 Zr 0.3 Cl 6 , Li 2.5 Gd 0.5 Zr 0.5 Cl 6 , Li 2.3 Gd 0.3 Zr 0.7 Cl 6 , Li 2.25 Gd 0.25 Zr 0.75 Cl 6 , Li 2.2 Gd 0.2 Zr 0.8 Cl 6 , Li 2.15 Gd 0.15 Zr 0.85 Cl 6 , Li 2.25 Gd 0.05 Zr 0.9 Cl 6 , or Li 2.1 Gd 0.1 Zr 0.9 Cl 6 , Li 2.05 Gd 0.05 Zr 0.95 Cl 6 .

4. The solid ion conductor of claim 1 , wherein the compound has a crystal structure belonging to a P3m1 space group or a P3m1-like space group.

5. The solid ion conductor of claim 1 , wherein
the compound represented by Formula 2 or Formula 3, when analyzed by X-ray diffraction using CuKα radiation, has a primary peak at a diffraction angle of about 31° 2θ to about 33° 2θ, and
secondary peaks at diffraction angle of about 15° 2θ to about 17° 2θ and about 40° 2θ to about 42° 2θ.

6. The solid ion conductor of claim 1 , wherein the compound of Formula 2 or Formula 3 has a primary peak at a diffraction angle of about 31° 2θ to about 33° 2θ that is shifted to a smaller angle than a corresponding peak of a Li 2 ZrCl 6 compound, when analyzed by X-ray diffraction using CuKα radiation.

7. The solid ion conductor of claim 1 , wherein the solid ion conductor has an ionic conductivity of about 2.1×10 −4 siemens per centimeter or more at about 25° C.

8. The solid ion conductor of claim 1 , wherein the solid ion conductor has an activation energy of about 0.27 electron volt to about 0.38 electron volt.

9. A solid electrolyte layer comprising: a layer comprising the solid ion conductor according to claim 1 .

10. A solid electrolyte comprising the solid ion conductor according to claim 1 and optionally an oxide solid ion conductor or a sulfide solid ion conductor.

11. An electrochemical device comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrolyte layer, wherein one or more of the positive electrode layer, the negative electrolyte layer, or the solid electrolyte layer comprises the solid ion conductor according to claim 1 .

12. The electrochemical device of claim 11 , further comprising a protective film on one or more of the positive electrode layer, the negative electrode layer, or solid electrolyte layer, wherein the protective film comprises the solid ion conductor.

13. The electrochemical device of claim 11 , wherein the positive electrode layer comprises one or more of a positive active material of a lithium transition metal oxide, a lithium transition metal phosphate, or a sulfide, and the solid ion conductor.

14. The electrochemical device of claim 11 , wherein the solid electrolyte layer comprises the solid ion conductor.

15. The electrochemical device of claim 11 , wherein the electrochemical device is an all-solid state secondary battery or a metal air battery.

16. A protected positive electrode, comprising
a positive electrode; and
a protective film comprising the solid ion conductor of claim 1 on the positive electrode.

17. A protected negative electrode, comprising
a negative electrode; and
a protective film comprising the solid ion conductor of claim 1 on the negative electrode.

18. A method of preparing a solid ion conductor, the method comprising: mechanically milling a solid ion conductor-forming precursor to form a solid ion conductor-forming precursor mixture; and
molding the solid ion conductor-forming precursor mixture to prepare a solid ion conductor comprising a compound having a distorted rock-salt type structure represented by Formula 2 or Formula 3:
Li 2+x M′ x Zr 1-x X y   Formula 2

wherein in Formula 2,
M′ is one or more of lanthanide metals having an oxidation state of +3 and a crystal ionic radius of about 104 picometers to about 109 picometers,
X is one or more halogen elements,
0<x<1, and 0<y<7,
Li p-q M q M′ r Zr 1-r X w   Formula 3

wherein in Formula 3,
M is one or more metals of Na, K, Cs, Cu, or Ag, and having an oxidation state of +1,
M′ is one or more lanthanide metals having an oxidation state of +3 and a crystal ionic radius of about 104 picometers to about 109 picometers,
X is one or more halogen elements,
1<p<3, 0≤q<1, 0<r<1, and 0<w<7.

19. The method of claim 18 , wherein the mechanical milling comprises one or more of ball milling, air-jet milling, bead milling, roll milling, planetary milling, hand milling, high-energy ball milling, stirred ball milling, vibrating milling, mechanofusion milling, shaker milling, attritor milling, disk milling, shape milling, nauta milling, nobilta milling, or high-speed mixing.

20. The method of claim 18 , wherein the mechanical milling is planetary milling and is performed at room temperature.

21. The method of claim 18 , further comprising, after the mechanically milling, conditioning the solid ion conductor-forming precursor mixture.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Kim Jusik
• Yoon Gabin

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M12/02

  Details (of electrodes H01M4/00; of non-active parts H01M50/00) · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title