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

Patent metadata

Field	Value
Publication number	US-11799129-B2
Application number	US-202117195889-A
Country	US
Kind code	B2
Filing date	Mar 9, 2021
Priority date	Mar 27, 2020
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

A solid ion conductor compound includes lithium (Li), phosphorus (P), hafnium (Hf), and sulfur (S), wherein if oxygen (O) is present, a content of the O is less than an amount of the Hf, and wherein the solid ion conductor compound has an argyrodite crystal structure, and in the argyrodite crystal structure the Hf is on a portion of the P crystallographic sites.

First claim

What is claimed is:

1. A solid ion conductor compound comprising:
Li, P, Hf, and S;
wherein the solid ion conductor compound does not comprise O,
wherein the solid ion conductor compound has an argyrodite crystal structure, and
in the argyrodite crystal structure the Hf is on a portion of the P crystallographic sites.

2. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has diffraction peaks at 15.42° 2θ±0.50°, 17.87° 2θ±0.50°, 25.48° 2θ±0.50°, 30.01° 2θ±0.50°, and 31.38° 2θ±0.50°, when measured by X-ray diffraction using CuKα radiation.

3. The solid ion conductor compound of claim 1 , further comprising at least one halogen element.

4. The solid ion conductor compound of claim 1 , further comprising, in addition to the Li, the P, and the Hf, at least one of a Group 1 element, a Group 2 element, a Group 4 element, a Group 5 element, a Group 6 element, a Group 11 element, a Group 14 element, or a Group 15 element.

5. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound is represented by Formula 1:
Li a M1 b M2 c P d Hf e S 6−f−g N g X f   Formula 1

wherein, in Formula 1,
X is at least one of a Group 17 element,
M1 is at least one of a Group 1 element, a Group 2 element, or a Group 11 element, wherein M1 is not Li,
M2 is at least one of a Group 4 element, a Group 5 element, a Group 6 element, a Group 14 element, or a Group 15 element, wherein M2 is not Hf, N, or P, and
4≤a≤8, 0≤b<1, 0≤c<1, 0<d<1, 0<e<1, 0<f<5, and 0≤g<1.

6. The solid ion conductor compound of claim 5 , wherein X is at least one of F, Cl, Br, or I.

7. The solid ion conductor compound of claim 5 , wherein 1≤f<3.

8. The solid ion conductor compound of claim 5 , wherein 0<e/(d+e)<0.5.

9. The solid ion conductor compound of claim 5 , wherein M1 is at least one of Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba, Ra, Cu, Ag, or Au.

10. The solid ion conductor compound of claim 5 , wherein M2 is at least one of Si, Ge, As, Sb, Bi, Sn, Pb, V, Nb, Ta, Cr, Mo, W, Ti, or Zr.

11. The solid ion conductor compound of claim 5 , wherein b=0 and c=0.

12. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound is represented by Formula 2:
Li 7+x−(v+y+z) P 1−x Hf x S 6−(v+y+z) N v X1 y X2 z   Formula 2

wherein, in Formula 2,
X1 and X2 are each independently at least one of F, Cl, Br, or I, and
0<x≤0.5, 0<y<2, 0<z<2, and 0≤v<1.

13. The solid ion conductor compound of claim 12 , wherein
X1 is Cl,
X2 is at least one of Cl or Br, and
0<y+z≤2.

14. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound has an ion conductivity retention of about 40 percent to about 100 percent, when measured after 14 days under a dry air atmosphere having a dew point of less than −40° C.

15. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound is represented by at least one of Li 7+x−y P 1−x Hf x S 6−y Cl y , Li 7+x−y P 1−x Hf x S 6−y Br y , Li 7+x−y P 1−x Hf x S 6−y I y , Li 7+x(y+z) P 1−x Hf x S 6−y−z Cl y Br z , Li 7+x−(y+z) P 1−x Hf x S 6−y−z Cl y I z , Li 7+x−(y+z) P 1−x Hf x S 6−y−z Br y I z , Li 7+x−(v+z) P 1−x Hf x S 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 x S 6−(v+y) N v I y , Li 7+x−(v+y+z) P 1−x Hf x S 6−(v+y+z) N v Cl y Br z , Li 7+x−(v+y+z) P 1−x Hf x S 6−(v+y+z) N v Cl y I z , or Li 7+x−(v+y+z) P 1−x Hf x S 6−(v+y+z) N v Br y I z ;
wherein in each of the foregoing formulas, x, y, z, and v are each independently 0<x≤0.5, 0<y<2, 0<z<2, and 0<v<1.

16. The solid ion conductor compound of claim 1 , wherein the solid ion conductor compound is at least one of 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 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 , or Li 5.7 P 0.9 Hf 0.1 N 0.1 S 4.4 Cl 0.5 Br.

17. A cathode active material layer comprising:
a cathode active material, and
the solid ion conductor compound of claim 1 on at least one surface of the cathode active material.

18. An electrochemical cell comprising:
a cathode layer comprising a cathode active material layer;
an anode layer comprising an anode active material layer; and
an electrolyte layer disposed between the cathode layer and the anode layer,
wherein at least one of the cathode active material layer or the electrolyte layer comprises the solid ion conductor compound of claim 1 .

19. The electrochemical cell of claim 18 , wherein the electrochemical cell is an all-solid secondary battery in which the combination of the cathode layer, the anode and the electrolyte layer have a vapor pressure of 0 atmosphere to about 2 atmospheres at 25° C.

20. The electrochemical cell of claim 18 , wherein the anode active material layer comprises an anode active material and a binder,
wherein the anode active material comprises amorphous carbon and at least one of Au, Pt, Pd, Si, Ag, Al, Bi, Sn, or Zn.

21. The electrochemical cell of claim 18 , further comprising a metal layer between the anode current collector and the anode active material layer, wherein the metal layer comprises lithium or a lithium alloy.

22. A method of preparing the solid ion conductor compound of claim 1 , the method comprising:
contacting a compound comprising lithium, a compound comprising Hf, a compound comprising P, and a compound comprising S to provide a mixture; and
heat-treating the mixture at a temperature of about 400° C. to about 700° C. in an inert atmosphere to provide the solid ion conductor compound of claim 1 .

23. The method of claim 22 , wherein the heat-treating of the mixture is performed at a temperature in a range of about 420° C. to about 600° C. for about 1 hour to about 36 hours.

24. A solid electrolyte comprising:
a solid ion conductor compound represented by Formula 1,
Li a M1 b M2 c P d Hf e S 6−f−g N g X f   Formula 1

wherein, in Formula 1,
X is at least one of a Group 17 element,
M1 is at least one of a Group 1 element, a Group 2 element, or a Group 11 element, wherein M1 is not Li,
M2 is at least one of a Group 4 element, a Group 5 element, a Group 6 element, a Group 14 element, or a Group 15 element, wherein M2 is not Hf, N, or P, and
4≤a≤8, 0≤b<1, 0≤c<1, 0<d<1, 0<e<1, 0<f<5, and 0≤g<1; and
at least one of a lithium sulfide, a silicon sulfide, a phosphorus sulfide, or a boron sulfide.

25. The solid electrolyte according to claim 24 , further comprising a binder, wherein the binder is at least one of styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or polyvinyl alcohol.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Kim Hyunseok
• Kim Soyeon
• Kitajima Shintaro

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M2300/008

  Halides · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title