Ceramics, methods for the production thereof and uses of same

Patent metadata

Field	Value
Publication number	US-11649190-B2
Application number	US-201917046912-A
Country	US
Kind code	B2
Filing date	May 30, 2019
Priority date	May 30, 2018
Publication date	May 16, 2023
Grant date	May 16, 2023

Abstract

This document describes processes for preparing ceramics, especially lithium-based ceramics. The ceramics produced by this process and their use in electrochemical applications are also described as well as electrode materials, electrodes, electrolyte compositions, and electrochemical cells comprising them.

First claim

The invention claimed is:

1. Process for preparing a lithium-based ceramic, the process comprising at least the steps of:
a) mixing a source of lithium ion, at least one metal oxide or phosphate and a carbon material to obtain a mixture of powders; and
b) heating the mixture of powders obtained in step (a) at a treatment temperature;
wherein the source of lithium ion used in step (a) has a melting point below the treatment temperature of step (b);
and wherein:
step (b) is carried out under inert atmosphere and the process further comprises a step (c) of heating the product of step (b) in the presence of oxygen for a period of time sufficient to eliminate the carbon material; or
step (b) is carried out in the presence of oxygen and for a period of time sufficient to eliminate the carbon material.

2. The process of claim 1 , which further comprises a step (b)(i) of mixing the product obtained in step (b) with a metal oxide or phosphate and a carbon material; and (b)(ii) heating the mixture obtained in (b)(i) at a second treatment temperature to obtain a second product, wherein the product of step (b) has a melting point above the treatment temperature of step (b)(ii).

3. The process of claim 1 , wherein:
the at least one metal oxide or phosphate is an oxide or phosphate of a metal selected from zirconium, titanium, germanium, gallium, tantalum, iron and niobium; or
the at least one metal oxide or phosphate comprises at least two, or at least three, metal oxides or phosphates of metals selected from lanthanum, aluminum, zirconium, titanium, germanium, gallium, tantalum, iron and niobium, provided that at least one metal is lanthanum or aluminum.

4. The process of claim 1 , wherein the at least one metal oxide or phosphate is an oxide of lanthanum or aluminum, the process further comprising a second metal oxide selected from zirconium oxide and titanium oxide, and optionally further comprising an oxide of an element selected from aluminium, germanium, gallium, tantalum, niobium, iron, barium, boron, and silicon.

5. The process of claim 1 , wherein the mixing (a) further comprises a phosphate salt.

6. The process of claim 1 , wherein the carbon material is selected from carbon black, graphene, graphite, carbon nanotubes, carbon fibers or nanofibers, and combinations thereof.

7. The process of claim 1 , wherein the heating step is performed at a temperature of in the range of 800 to 1400° C.

8. The process of claim 1 , wherein the mixing is performed by ball milling or in a planetary mixer.

9. The process of claim 1 , wherein said ceramic has a residual carbon content below 10 wt. %.

10. The process of claim 9 , wherein said ceramic comprises a compound selected from the compounds of Formulae (I) to (IV):
Li 7 La 3 Zr 2 O 12   (I)

Li 7-x La 3 Zr 2 M x O 12   (II)

Li 3y La (2/3)-y Ti 1-y′ M y y′ O 3   (Ill)

Li 1+z Al z M x 2-z (PO 4 ) 3   (IV)

wherein:
M is selected from Al, Ga, Ta, Fe, and Nb;
M x is selected from Ti and Ge;
M y is selected from Ba, B, Al, Si and Ta;
x is greater than 0 and less than or equal to 1;
y is greater than 0 and less than or equal to 0.67;
y′ is within the range of 0 to less than 1; and
z is within the range of 0 to 1;
wherein the compound may further comprise ionic vacancies.

11. The process of claim 10 , wherein the compound is of Formula (I) or Formula (II).

12. The process of claim 10 , wherein the compound is of Formula (III) or of Formula (IV).

13. The process of claim 11 , wherein the compound is an undoped compound of Formula (I) having a cubic crystal structure.

14. The process of claim 1 , wherein the lithium ion:carbon molar ratio being in the range of 0.5 to 2.4.

15. The process of claim 1 , wherein said oxygen is present in air.

16. The process of claim 4 , wherein the at least one metal oxide or phosphate is a lanthanum oxide.

17. The process of claim 6 , wherein said carbon black is acetylene black.

18. The process of claim 1 , wherein the heating step is performed for a period of time in the range of 30 minutes to 3 hours.

19. The process of claim 18 , wherein the heating step is performed for a period of time in the range of 45 minutes to 1.5 hours.

20. The process of claim 18 , wherein the heating step is performed for a period of time of about 1 hour.

21. The process of claim 8 , wherein the mixing is performed by ball milling.

22. The process of claim 8 , wherein the mixing is performed by ball milling performed in a zirconium dioxide container using zirconium dioxide balls.

23. The process of claim 9 , wherein said ceramic has a residual carbon content below 5 wt. %.

24. The process of claim 11 , wherein the compound of Formula (I) or Formula (II) has a tetragonal crystal structure or a cubic crystal structure.

25. The process of claim 12 , wherein the compound is of Formula (III) and has a perovskite-type crystal structure.

26. The process of claim 12 , wherein the compound is of Formula (IV) and has a NASICON-type crystal structure.

Assignees

• Hydro Quebec

Inventors

• Paolella Andrea
• Savoie Sylvio
• Gariepy Vincent
• Zhu Wen
• Guerfi Abdelbast
• Zaghib Karim

Classifications

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• C04B2235/425

  Graphite · CPC title

• C04B35/447 Primary

  based on phosphates {, e.g. hydroxyapatite} · CPC title

• C04B35/49

  containing also titanium oxides or titanates · CPC title