Additive to ceramic ion conducting material to mitigate the resistive effect of surface carbonates and hydroxides

Patent metadata

Field	Value
Publication number	US-11094996-B2
Application number	US-201916575143-A
Country	US
Kind code	B2
Filing date	Sep 18, 2019
Priority date	Sep 18, 2019
Publication date	Aug 17, 2021
Grant date	Aug 17, 2021

Abstract

A method of modifying a carbonate layer formed on a surface of an electrochemical cell component is provided. The surface includes a ceramic oxide. The carbonate layer includes a carbonate and is substantially non-conductive to lithium ions and sodium ions. The method includes contacting the carbonate layer with a modifying agent to form a mixture and causing the modifying agent to incorporate into the carbonate layer and form a modified hybrid layer including a eutectic mixture of the modifying agent and the carbonate. The modified hybrid layer is conductive to lithium ions and sodium ions.

First claim

What is claimed is:

1. A method of modifying a carbonate layer formed on a surface of an electrochemical cell component, the surface comprising a ceramic oxide and the carbonate layer comprising a carbonate and being substantially non-conductive to lithium ions, sodium ions, or a combination thereof, the method comprising:
contacting the carbonate layer with a modifying agent to form a mixture; and
causing the modifying agent to incorporate into the carbonate layer and to form a modified hybrid layer comprising a eutectic mixture of the modifying agent and the carbonate, the modified hybrid layer being conductive to lithium ions, sodium ions, or a combination thereof.

2. The method according to claim 1 , wherein the modifying agent comprises MX, where M is an alkali metal and X is a halide.

3. The method according to claim 2 , wherein the modifying agent comprises LiF or NaF.

4. The method according to claim 1 , wherein the causing the modifying agent to incorporate into the carbonate layer comprises heating the mixture at a temperature greater than or equal to about 300° C.

5. The method according to claim 4 , wherein the heating comprises heating the mixture at a temperature greater than or equal to about 300° C. to less than or equal to about 400° C.

6. The method according to claim 4 , wherein the electrochemical cell component is a green solid-state electrolyte and the heating comprises sintering the mixture at a temperature greater than or equal to about 600° C. to less than or equal to about 1200° C. to form a densified solid-state electrolyte structure.

7. The method according to claim 6 , wherein the green solid-state electrolyte comprises a plurality of ceramic oxide-based solid-state electrolyte particles in powder form, wherein at least a portion of each solid-state electrolyte particle of the plurality is coated with the carbonate layer.

8. The method according to claim 1 , wherein the ceramic oxide comprises Li 7 La 3 Zr 2 O 12 (LLZO), Li x La y TiO 3 where 0<x<1 and 0<y<1 (LLTO), Li 1+x Al y Ti 2−y PO 4 where 0<x<1 and 0<y<2 (LATP), Li 2+2x Zn 1−x GeO 4 where 0<x<1 (LISICON), Li 2 PO 2 N (LIPON), sodium equivalents thereof, or combinations thereof and the ceramic oxide is optionally doped with aluminum, tantalum, niobium, gallium, indium, tin, antimony, bismuth, yttrium, germanium, calcium, strontium, barium, hafnium, or combinations thereof.

9. The method according to claim 1 , wherein the carbonate comprises lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), or a combination thereof.

10. The method according to claim 1 , wherein the contacting and the causing the modifying agent to incorporate into the carbonate layer are performed substantially simultaneously by atomic layer deposition.

11. The method according to claim 1 , wherein the electrochemical cell component comprising the modified hybrid layer is substantially free of electronically conductive carbon residues.

12. The method according to claim 1 , further comprising:
pressing the mixture in a die defining a predetermined shape; and
performing the heating during the pressing.

13. The method according to claim 1 , wherein the electrochemical cell component is a separator comprising the ceramic oxide or a coating comprising the ceramic oxide disposed on a polymeric separator.

14. The method according to claim 1 , further comprising:
incorporating the electrochemical cell component into an electrochemical cell.

15. A method of modifying a carbonate layer formed on a surface of an electrochemical cell component, the surface comprising a ceramic oxide and the carbonate layer comprising lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), or a combination thereof and being substantially non-conductive to lithium ions, sodium ions, or a combination thereof, the method comprising:
contacting the carbonate layer of with a modifying agent comprising MX, where M is Na or Li and X is a halide, to form a mixture;
pressing the mixture in a die defining a predetermined shape; and
during the pressing, heating the mixture at a temperature greater than or equal to about 300° C. to incorporate the MX into the carbonate layer and to form a modified hybrid layer comprising a eutectic mixture of the MX and the Li 2 CO 3 , Na 2 CO 3 , or combination thereof, the modified hybrid layer being conductive to lithium ions, sodium ions, or a combination thereof.

16. The method according to claim 15 , wherein the predetermined shape is a wafer, a disk, a sheet, a parallelepiped, a cylinder, a cube, a sphere, or a pellet.

17. The method according to claim 15 , wherein the electrochemical cell component is a solid-state electrolyte, a separator, a coating disposed on a separator, a positive electrode comprising a positive electrode active material having a solid-state electrolyte comprising the ceramic oxide embedded therein, or a negative electrode comprising a negative electrode active material having a solid-state electrolyte comprising the ceramic oxide embedded therein.

18. A method of modifying a carbonate layer formed on a surface of an electrochemical cell component, the surface comprising a ceramic oxide and the carbonate layer comprising lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), or a combination thereof and being substantially non-conductive to ions, the method comprising:
contacting the carbonate layer of with a modifying agent comprising LiF, NaF, or a combination thereof to form a mixture; and
causing the modifying agent to incorporate into the carbonate layer and to form a modified hybrid layer comprising a eutectic mixture of the LiF, NaF, or the combination thereof and the carbonate, the modified hybrid layer having an ionic conductivity of greater than or equal to about 0.1 mS,
wherein the ceramic oxide is optionally doped and comprises Li 7 La 3 Zr 2 O 12 (LLZO), Li x La y TiO 3 where 0<x<1 and 0<y<1 (LLTO), Li 1+x Al y Ti 2−y PO 4 where 0<x<1 and 0<y<2 (LATP), Li 2+2x Zn 1−x GeO 4 where 0<x<1 (LISICON), Li 2 PO 2 N (LIPON), sodium equivalents thereof, or combinations thereof, and
wherein the electrochemical cell component is a solid-state electrolyte, a separator, or a coating disposed on a separator.

19. The method according to claim 18 , wherein the causing the modifying agent to incorporate into the carbonate layer comprises heating the mixture at a temperature greater than or equal to about 300° C. or the contacting and the causing the modifying agent to incorporate into the carbonate layer are performed substantially simultaneously by atomic layer deposition.

20. The method according to claim 18 , wherein the electrochemical cell component is a separator comprising the ceramic oxide, a coating comprising the ceramic oxide disposed on a polymeric separator, or a solid-state electrolyte comprising the ceramic oxide, and the method further comprises:
disposing the electrochemical cell component between a negative electrode comprising negative electrode active particles and a positive electrode comprising positive electrode active particles,
wherein the negative electrode active particles and the positive electrode active articles are independently mixed with no electrolyte, with solid-state electrolyte particles, or with a liquid electrolyte solution.

Assignees

• Gm Global Tech Operations Llc

Inventors

• Xiao Xingcheng
• Schmidt Robert D

Classifications

• H01M50/449

  having a layered structure · CPC title

• H01M50/403 Primary

  Manufacturing processes of separators, membranes or diaphragms · CPC title

• H01M50/451 Primary

  comprising layers of only organic material and layers containing inorganic material · CPC title

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M4/1393

  of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title