Liquid metal interfacial layers for solid electrolytes and methods thereof

Patent metadata

Field	Value
Publication number	US-11404698-B2
Application number	US-201916668904-A
Country	US
Kind code	B2
Filing date	Oct 30, 2019
Priority date	Oct 30, 2019
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

Methods of making a solid-state electrochemical cell that cycles lithium ions are provided that include applying a liquid metal composition comprising gallium to a first major surface of either a solid-state electrolyte or a solid electrode (e.g., lithium metal) in the presence of an oxidant and in an environment substantially free of water to reduce surface tension of the liquid metal composition so that it forms a continuous layer over the first major surface. The first major surface having the continuous layer of liquid metal composition is contacted with a second major surface to form a continuous interfacial layer between the solid-state electrolyte and the solid electrode. Solid-state electrochemical cells formed by such methods are also provided, where the metal composition comprising gallium is a liquid in a temperature range of greater than or equal to about 20° C. to less than or equal to about 30° C.

First claim

What is claimed is:

1. A method of making a solid-state electrochemical cell that cycles lithium ions, the method comprising:
applying a liquid metal composition comprising gallium that is a liquid at least within a temperature range of greater than or equal to about 20° C. to less than or equal to about 30° C. to a first major surface of either a solid-state electrolyte or a solid electrode in the presence of an oxidant and in an environment substantially free of water to reduce surface tension of the liquid metal composition so that it forms a continuous layer over the first major surface; and
contacting the first major surface having the continuous layer of liquid metal composition with a second major surface of the other of the solid-state electrolyte or the solid electrode, such that the continuous layer defines an interfacial layer between the solid-state electrolyte and the solid electrode and contacts all of the first major surface and the second major surface.

2. The method of claim 1 , wherein the solid-state electrolyte is heated prior to or during the applying.

3. The method of claim 1 , wherein the applying is a process selected from the group consisting of: thermal evaporation, doctor blade coating, and combinations thereof.

4. The method of claim 1 , wherein during the applying, a surface tension of the liquid metal composition is less than or equal to about 100 mN/m.

5. The method of claim 1 , wherein a contact angle of the liquid metal composition on the first major surface is less than or equal to about 90°.

6. The method of claim 1 , wherein a contact angle of the liquid metal composition on the first major surface is less than or equal to about 5°.

7. The method of claim 1 , wherein the interfacial layer has a thickness of greater than or equal to about 5 nm to less than or equal to about 20 micrometers.

8. The method of claim 1 , wherein the solid-state electrolyte comprises a material selected from the group consisting of: 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), Li x La 2/3−x TiO 3 , Li 1+x Al x Ti 2−x (PO 4 ) 3 , Li 10 GeP 2 S 12 , and combinations thereof and the solid electrode comprises lithium.

9. The method of claim 1 , wherein the liquid metal composition comprising gallium is elemental gallium or an alloy of gallium and a metal selected from the group consisting of: tin, zinc, indium, bismuth, and combinations thereof.

10. The method of claim 1 , wherein the liquid metal composition comprising gallium is selected from the group consisting of: GaSn, GaInSn, GaSn 8 , GaSn 12 , GaZn 5 , Ga 75 In 25 , GaIn 25 Sn 13 , Ga 69.8 In 17.6 Sn 12.6 , Ga 62.5 In 21.5 Sn 16 , GaSn 60 In 10 , GaIn 29 Zn 4 , GaZn 16 In 12 , Ga 66 In 20.5 Sn 13.5 , Ga 61 In 25 Sn 13 Zn 1 , GaIn 15 Sn 13 Zn 1 , Ga 66.4 In 20.9 Sn 9.7 Zn 3 , Ga 68 In 21 Sn 9.5 Bi 1.5 , Ga 68 In 21 Sn 9.5 Bi 0.75 Zn 0.75 , and combinations thereof.

11. A solid-state electrochemical cell that cycles lithium ions, the electrochemical cell comprising:
a solid-state electrolyte defining a first major surface;
a solid electrode comprising an electroactive material and defining a second major surface; and
an interfacial layer disposed between and coextensive with the first major surface of the solid-state electrolyte and the second major surface of the solid electrode, wherein the interfacial layer is formed of a metal composition comprising gallium that is a liquid at least within a temperature range of greater than or equal to about 20° C. to less than or equal to about 30° C. and is continuous and contacts all of the first major surface and the second major surface.

12. The solid-state electrochemical cell of claim 11 , wherein the solid electrode comprises lithium metal.

13. The solid-state electrochemical cell of claim 11 , wherein the solid-state electrolyte comprises a material selected from the group consisting of: 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), Li x La 2/3−x TiO 3 , Li 1+x Al x Ti 2−x (PO 4 ) 3 , Li 10 GeP 2 S 12 , and combinations thereof and the solid electrode comprises lithium.

14. The solid-state electrochemical cell of claim 11 , wherein the interfacial layer has a thickness of greater than or equal to about 5 nm to less than or equal to about 20 micrometers.

15. The solid-state electrochemical cell of claim 11 , wherein the interfacial layer has a resistivity of less than or equal to about 2 Ohm/cm 2 .

16. The solid-state electrochemical cell of claim 11 , wherein exposed surfaces of the interfacial layer comprise metal oxides.

17. The solid-state electrochemical cell of claim 11 , wherein the metal composition comprising gallium is selected from the group consisting of: GaSn, GaInSn, GaSn 8 , GaSn 12 , GaZn 5 , Ga 75 In 25 , GaIn 25 Sn 13 , Ga 69.8 In 17.6 Sn 12.6 , Ga 62.5 In 21.5 Sn 16 , GaSn 60 In 10 , GaIn 29 Zn 4 , GaZn 16 In 12 , Ga 66 In 20.5 Sn 13.5 , Ga 61 In 25 Sn 13 Zn 1 , GaIn 15 Sn 13 Zn 1 , Ga 66.4 In 20.9 Sn 9.7 Zn 3 , Ga 68 In 21 Sn 9.5 Bi 1.5 , Ga 68 In 21 Sn 9.5 Bi 0.75 Zn 0.75 , and combinations thereof.

18. The solid-state electrochemical cell of claim 11 , wherein the interfacial layer comprising the metal composition is substantially free of any other components.

19. The solid-state electrochemical cell of claim 11 , wherein the temperature range is greater than or equal to about −20° C. to less than or equal to about 150° C.

20. A solid-state electrochemical cell that cycles lithium ions, the electrochemical cell comprising:
a solid-state electrolyte defining a first major surface and an opposite second major surface;
a negative solid electrode comprising a negative electroactive material and defining a third major surface;
a positive solid electrode comprising a positive electroactive material and defining a fourth major surface;
a first interfacial layer disposed between and coextensive with the first major surface of the solid-state electrolyte and the third major surface of the negative solid electrode, a second interfacial layer disposed between and coextensive with the second major surface of the solid-state electrolyte and the fourth major surface of the positive solid electrode, wherein the first interfacial layer and the second interfacial layer are formed of a metal composition comprising gallium that is a liquid in a temperature range of greater than or equal to about 20° C. to less than or equal to about 30° C.

Assignees

• Gm Global Tech Operations Llc

Inventors

• Xu Jiagang
• Xiao Xingcheng
• Schmidt Robert D

Classifications

• H01M4/139

  Processes of manufacture · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/0562

  Solid materials · CPC title

• H01M2300/0068

  inorganic · CPC title