Surface protection of lithium metal anode

Patent metadata

Field	Value
Publication number	US-2020343533-A1
Application number	US-201916658286-A
Country	US
Kind code	A1
Filing date	Oct 21, 2019
Priority date	Apr 26, 2019
Publication date	Oct 29, 2020
Grant date	—

Abstract

A method and apparatus for forming metal electrode structures, more specifically lithium-containing anodes, high performance electrochemical devices, such as primary and secondary electrochemical devices, including the aforementioned lithium-containing electrodes. In one implementation, the method comprises forming a lithium metal film on a current collector. The current collector comprises copper and/or stainless steel. The method further comprises forming a protective film stack on the lithium metal film, comprising forming a first protective film on the lithium metal film. The first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

First claim

1 . A method, comprising:
forming a lithium metal film on a current collector, wherein the current collector comprises copper and/or stainless steel; and forming a protective film stack on the lithium metal film, comprising:
forming a first protective film on the lithium metal film, wherein the first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

2 . The method of claim 1 , wherein forming the protective film stack further comprises forming a second protective film on the first protective film, the second protective film selected from a lithium fluoride (LiF) film, a metallic film, a carbon-containing film, or a combination thereof.

3 . The method of claim 2 , wherein the dielectric film is selected from oxides of: titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or a combination thereof.

4 . The method of claim 2 , wherein the bismuth chalcogenide film and the copper chalcogenide film are selected from CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 , Bi 2 Se 3 , or a combination thereof.

5 . The method of claim 2 , wherein the metallic film is selected from tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper (Cu), silver (Ag), gold (Au), or a combination thereof.

6 . The method of claim 4 , wherein the first protective film is the bismuth chalcogenide film or the copper chalcogenide film and the second protective film is lithium fluoride.

7 . The method of claim 4 , wherein the first protective film is the bismuth chalcogenide film or the copper chalcogenide film and the second protective film is the metallic film.

8 . The method of claim 4 , wherein the first protective film is the lithium fluoride film and the second protective film is the carbon-containing film.

9 . The method of claim 1 , wherein the first protective film has a thickness of 100 nanometers or less.

10 . The method of claim 1 , further comprising exposing the current collector to a plasma treatment or corona discharge process to remove organic materials from exposed surfaces of the current collector prior to forming the lithium metal film on the current collector.

11 . The method of claim 1 , wherein forming the first protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an e-beam evaporation process, and a chemical vapor deposition (CVD) process.

12 . The method of claim 2 , wherein forming the second protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an e-beam evaporation process, and a chemical vapor deposition (CVD) process.

13 . An anode electrode structure, comprising:
a current collector comprising copper and/or stainless steel, a lithium metal film formed on the current collector; and a protective film stack formed on the lithium metal film, comprising:
a first protective film formed on the lithium metal film, wherein the first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof; and
a second protective film formed on the first protective film, the second protective film selected from a lithium fluoride (LiF) film, a metallic film, a carbon-containing film, or a combination thereof.

14 . The anode electrode structure of claim 13 , wherein the dielectric film is selected from oxides of: titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or a combination thereof.

15 . The anode electrode structure of claim 13 , wherein the bismuth chalcogenide film and the copper chalcogenide film are selected from CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 , Bi 2 Se 3 , or a combination thereof.

16 . The anode electrode structure of claim 13 , wherein the metallic film is selected from tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper (Cu), silver (Ag), gold (Au), or a combination thereof.

17 . The anode electrode structure of claim 13 , wherein the first protective film is the bismuth chalcogenide film or the copper chalcogenide film and the second protective film is lithium fluoride.

18 . The anode electrode structure of claim 13 , wherein the first protective film is the bismuth chalcogenide film or the copper chalcogenide film and the second protective film is the metallic film.

19 . An energy storage device, comprising:
the anode electrode structure of claim 14 ; a cathode electrode structure; and a solid electrolyte film formed between the anode electrode structure and the cathode electrode structure.

20 . The energy storage device of claim 19 , wherein the solid electrolyte film is comprised of one or more of: LiPON, doped variants of either crystalline or amorphous phases of Li 7 La 3 Zr 2 O 12 , doped anti-perovskite compositions, argyrodite compositions, lithium-sulfur-phosphorous materials, Li 2 S—P 2 S 5 , Li 10 GeP 2 S 12 , and Li 3 PS 4 , lithium phosphate glasses, (1−x)LiI-(x)Li 4 SnS 4 , xLiI-(1−x)Li 4 SnS 4 , mixed sulfide and oxide electrolytes (crystalline LLZO, amorphous (1−x)LiI-(x)Li 4 SnS 4 mixture, amorphous xLiI-(1−x)Li 4 SnS 4 ), Li 3 S(BF 4 ) 0.5 Cl 0.5 , Li 4 Ti 5 O 12 , lithium doped lanthanum titanate (LATP), Li 2+2x Zn 1−x GeO 4 , LiTi 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and a combination thereof.

Assignees

• Applied Materials Inc

Inventors

• Herle Subramanya P

Classifications

• H01M10/0562

  Solid materials · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/669

  Steels · CPC title

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title