Protected anode, lithium air battery including the same, and method of preparing ion conductive protective layer

Patent metadata

Field	Value
Publication number	US-9917304-B2
Application number	US-201314106785-A
Country	US
Kind code	B2
Filing date	Dec 15, 2013
Priority date	Dec 21, 2012
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

A protected anode including: an anode including lithium or capable of reversibly incorporating lithium ions; and a lithium ion-conductive protective layer on the anode and including a ceramic composite represented by Formula 1:

Li 1+a Al b Ge 2−c M d P 3+e O 12+f   Formula 1

wherein M is at least one element selected from titanium (Ti), zirconium (Zr), and germanium (Ge), 0≦a≦1, 0≦b≦1, 0≦c≦1, 0≦d≦0.5, 0≦e≦0.1, and 0≦f≦1.

First claim

What is claimed is:

1. A protected anode comprising:
an anode including lithium or a material capable of reversibly incorporating lithium ions; and
a lithium ion-conductive protective layer on the anode and comprising a ceramic composite represented by Formula 1:
Li 1+a Al b Ge 2−c M d P 3+e O 12+f   Formula 1

wherein M is at least one element selected from titanium (Ti), zirconium (Zr), and germanium (Ge), 0≦a≦1, 0≦b≦1, 0≦c≦1, 0≦d≦0.5, 0≦e≦0.1, and 0≦f≦1.

2. The protected anode of claim 1 , wherein the ceramic composite is represented by Formula 2 below:
Li 1.4+a′ Al 0.4+b′ Ge 1.6+c′ M d′ P 3+e′ O 12+f′   Formula 2

wherein M is at least one element selected from titanium (Ti), zirconium (Zr), and germanium (Ge), −0.1≦a′≦0.1, −0.1≦b′≦0.1, −0.1≦c′≦0.1, 0.04≦d′≦0.4, 0≦e′≦0.1, and 0≦f≦0.9.

3. The protected anode of claim 1 , wherein the lithium ion-conductive protective layer is porous.

4. The protected anode of claim 3 , wherein the lithium ion-conductive protective layer further comprises a cross-linkable first polymer, which is disposed in pores of the lithium ion-conductive protective layer.

5. The protected anode of claim 4 , wherein the cross-linkable first polymer is a thermoset.

6. The protected anode of claim 4 , wherein the cross-linkable first polymer comprises at least one selected from an epoxy, an acryl, a polyamide, a polyimide, a polyimide amide, a polycarbonate, a polyester, a phenol, a polyurethane, and a melamine.

7. The protected anode of claim 4 , wherein the cross-linkable first polymer has a lithium ion conductivity of about 10 −4 Siemens per centimeter or less.

8. The protected anode of claim 4 , wherein an amount of the cross-linkable first polymer is from about 0.01 parts to about 20 parts by weight, based on 100 parts by weight of the lithium ion-conductive protective layer.

9. The protected anode of claim 1 , wherein the lithium ion-conductive protective layer has a thickness of from about 1 micrometer to about 500 micrometer.

10. The protected anode of claim 1 , wherein the lithium ion-conductive protective layer has a moisture permeability equivalent to pass about 100 milligrams per liter or less of Cl − ions per day.

11. The protected anode of claim 1 , further comprising an intermediate layer between the anode and the lithium ion-conductive protective layer, the intermediate layer comprising at least one selected from a liquid electrolyte including a separator, a non-aqueous solvent, and a lithium salt; an inorganic solid electrolyte membrane; a polymer solid electrolyte membrane; a gel solid electrolyte membrane; and a lithium ion-conductive solid electrolyte membrane.

12. The protected anode of claim 11 , wherein the at least one intermediate layer further comprises an insulating inorganic filler.

13. The protected anode of claim 11 , wherein the separator comprises at least one selected from a polyethylene oxide-based polymer, a polypropylene-based polymer, a polyacrylonitrile-based polymer, a polyvinylidene-fluoride-based polymer, and a polymethylmethacrylate-based polymer.

14. The protected anode of claim 11 , wherein the lithium salt comprises at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) wherein x and y are natural numbers, LiF, LiBr, LiCl, LiI, and lithium bis(oxalato) borate.

15. The protected anode of claim 12 , wherein the insulating inorganic filler is selected from the group consisting of SiO 2 , BaTiO 3 , TiO 2 , Al 2 O 3 , and Li 2 CO 3 .

16. The protected anode of claim 11 , wherein the at least one intermediate layer has an ionic conductivity of about 2×10 −3 Siemens per centimeter or greater, a lithium ion transfer coefficient of about 0.16 or greater, and a lithium ion mobility of about 1.1×10 −6 square centimeters per volt-seconds or greater.

17. A lithium air battery comprising:
the protected anode of claim 1 ; and
a cathode using oxygen as a cathode active material.

18. A method of manufacturing a protected anode according to claim 1 , the method comprising:
providing an anode including lithium or a material capable of reversibly incorporating lithium ions; and
preparing a lithium ion-conductive protective layer on the anode,
wherein the preparing comprises:
thermally treating a mixture of a ceramic compound represented by Formula 3
Li 1+a″ Al b″ Ge 2−c″ P 3+e″ O 12+f″   Formula 3

wherein 0≦a″≦1, 0≦b″≦1, 0≦c″≦1, 0≦e″≦0.1, and 0≦f″≦1, and at least one inorganic oxide selected from TiO 2 , ZnO 2 , and GeO 2 to obtain a thermal-treatment product;
shaping the thermal-treatment product to prepare a film; and
thermally treating the film to obtain the lithium ion-conductive protective layer.

19. The method of claim 18 , wherein the ceramic compound of Formula 3 is at least one selected from Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 , Li 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 1.6 Al 0.6 Ge 1.4 (PO 4 ) 3 , and Li 1.7 Al 0.7 Ge 1.3 (PO 4 ) 3 .

20. The method of claim 18 , further comprising filling pores in the lithium ion-conductive protective layer with a cross-linkable polymer.

Assignees

• Samsung Electronics Co Ltd
• National Univ Corporation Mie Univ

Inventors

• Lee Dong-Joon
• Im Dong-Min
• Roev Victor
• Ma Sang-Bok
• Park Min-Sik
• Yamamoto Osamu
• Imanishi Nobuyuki
• Choi Won-Sung
• Takeda Yasuo

Classifications

• 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

• H01M12/065

  with plate-like electrodes or stacks of plate-like electrodes · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/622

  being polymers · CPC title

• H01M4/366 Primary

  as layered products · CPC title