Lithium metal sulfide and lithium metal sulfide argyrodite ionically conductive compounds and related uses

Patent metadata

Field	Value
Publication number	US-12129171-B2
Application number	US-202117558782-A
Country	US
Kind code	B2
Filing date	Dec 22, 2021
Priority date	May 24, 2017
Publication date	Oct 29, 2024
Grant date	Oct 29, 2024

Abstract

Articles, compositions, and methods involving ionically conductive compounds are provided. In some embodiments, the ionically conductive compounds are useful for electrochemical cells. The disclosed ionically conductive compounds may be incorporated into an electrochemical cell (e.g., a lithium-sulfur electrochemical cell, a lithium-ion electrochemical cell, an intercalated-cathode based electrochemical cell) as, for example, a protective layer for an electrode, a solid electrolyte layer, and/or any other appropriate component within the electrochemical cell. In certain embodiments, electrode structures and/or methods for making electrode structures including a layer comprising an ionically conductive compound described herein are provided.

First claim

What is claimed is:

1. An article for use in an electrochemical cell, comprising:
a compound of formula (I):
Li x M y Q w P z S u X t   (I)

wherein:
M is selected from the group consisting of Fe, Mg, Ag, Cu, Zr, and Zn,
Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, As, and combinations thereof, and wherein Q, when present, is different than M,
X is selected from the group consisting of halide and pseudohalide,
x is 8-22,
y is 0.1-3,
w is 0-3,
z is 0.1-3,
u is 7-20, and
t is 0.1-8.

2. An article as in claim 1 , wherein Q is present, wherein Q is a combination of two or more atoms selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, and Al, and wherein the stoichiometric ratio of each atom in Q is such that the total amount of atoms present in Q is w and is 0-3.

3. An article as in claim 1 , wherein the compound has an argyrodite-type crystal structure.

4. An article as in claim 3 , wherein Q is present, and at least a portion of Q, and P are tetrahedrally coordinated in the argyrodite-type crystal structure.

5. An article as in claim 3 , wherein at least a portion of Li and at least a portion of M occupy a Rietveld Refinement lithium lattice site on the crystal structure.

6. An article as in claim 5 , wherein at least a portion of Li and at least a portion of M occupy a Rietveld Refinement 48 h lattice site on the crystal structure.

7. An article as in claim 1 , comprising a layer comprising the compound of formula (I).

8. An article as in claim 1 , comprising the compound of formula (I) deposited on a layer.

9. An article as in any preceding claim , wherein M is monovalent.

10. An article as in claim 1 , wherein M is bivalent.

11. An article as in claim 1 , wherein M is Fe.

12. An article as in claim 1 , wherein the article comprises a plurality of particles comprising the compound of formula (I).

13. An electrochemical cell comprising the article in claim 1 .

14. An electrochemical cell as in claim 13 , further comprising a liquid electrolyte.

15. An electrochemical cell as in claim 13 , comprising an anode comprising lithium or silicon.

16. An electrochemical cell as in claim 13 , comprising a cathode comprising sulfur.

17. An electrochemical cell as in claim 13 , comprising a cathode comprising a lithium-intercalation species.

18. A method for forming a composition, comprising:
heating a mixture of precursors comprising atoms of the elements Li, S, P, M, optionally Q, and X, to a temperature ranging from 500° C. to 1200° C. for a duration ranging from 3 hours to 24 hours;
cooling the mixture; and
forming a composition comprising a compound of formula (I) having an argyrodite-type crystal structure:
Li x M y Q w P z S u X t   (I)

wherein:
M is selected from the group consisting of Fe, Mg, Ag, Cu, Zr, and Zn,
Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, and combinations thereof, and wherein Q, when present, is different than M,
X is selected from the group consisting of halide and pseudohalide,
x is 8-22,
y is 0.1-3,
w is 0-3,
z is 0.1-3,
u is 7-20, and
t is 0.1-8.

19. A method as in claim 18 , wherein:
the mixture of precursors comprises at least two of Li 2 S, MS a , P b S c , QS d , LiX, Q, and S, wherein:
a is 0-8;
b is 0-2;
c is 0-8, such that b+c is 1 or greater; and
d is 0-3.

Assignees

• Sion Power Corp
• Basf Se

Inventors

• Schneider Holger
• Du Hui
• Leitner Klaus
• Ter Maat Johan
• Hartmann Pascal
• Kulisch Joern
• Safont-Sempere Marina
• Kelley Tracy Earl
• Scordilis-Kelley Chariclea

Classifications

• H01B1/10

  sulfides · CPC title

• C01B17/22

  Alkali metal sulfides or polysulfides · CPC title

• H01M50/449

  having a layered structure · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M50/434

  Ceramics · CPC title